Glass articles having a blackened layer and methods of making the same

Abstract

The present application provides a glass product with blackened layer, which contains, in terms of weight percentage, SiO2: 51-68%; B2O3: 6-19%; BaO: 6-19%; ZnO: 1-10%; K2O: 0.5-10%; Na2O: more than 0 but less than or equal to 8%; Sb2O3: more than 0 but less than or equal to 2%, wherein SiO2 / BaO is 3.0-11.0. Through reasonable component design, the glass product with blackened layer of the present application has a suitable coefficient of thermal expansion. In some embodiments, the coefficient of thermal expansion of the glass product with blackened layer obtained by the present application can be matched with gallium arsenide material.

Description

Technical Field

[0001] This invention relates to a glass article with a blackened layer, and more particularly to a glass article with a blackened layer having a suitable coefficient of thermal expansion and a method for manufacturing the same. Background Technology

[0002] Glass products with a blackened layer are transparent glasses with a blackened surface, such as anti-halo stepped glass. Anti-halo stepped glass is mainly used in image intensifiers of low-light night vision devices, serving as the input window of a single-stage image intensifier to eliminate stray light and deposit multi-alkali photocathodes. Because the blackened layer of the glass absorbs incident and reflected light, it eliminates scattered light from streaks, bubbles, and other defects, as well as reflected light from the optical path system, significantly improving the image resolution and sensitivity of low-light night vision devices. Anti-halo stepped glass requires excellent visible light transmittance in the transparent area and lower visible light transmittance in the blackened area. Furthermore, the coefficient of thermal expansion of the anti-halo stepped glass is crucial; it needs to match the coefficient of thermal expansion of gallium arsenide materials to prevent separation of bonded components due to temperature changes, which would reduce the image resolution and sensitivity of optical instruments such as low-light night vision devices. Therefore, for glass products with a blackened layer, a coefficient of thermal expansion that is too high or too low is detrimental to their application. Developing a glass product with a blackened layer and a suitable coefficient of thermal expansion is of great significance for promoting the development of optical instruments. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to provide a glass product with a blackening layer and a suitable coefficient of thermal expansion.

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

[0005] (1) Glass products with a blackening layer, the composition of which is expressed as a weight percentage, contains: SiO2: 51-68%; B2O3: 6-19%; BaO: 6-19%; ZnO: 1-10%; K2O: 0.5-10%; Na2O: greater than 0 but less than or equal to 8%; Sb2O3: greater than 0 but less than or equal to 2%, wherein the SiO2 / BaO ratio is 3.0-11.0.

[0006] (2) The glass article with a blackened layer according to (1) further comprises, by weight percentage: Bi2O3: 0-4%; and / or Al2O3: 0-8%; and / or SrO: 0-5%; and / or MgO: 0-5%; and / or CaO: 0-5%; and / or Li2O: 0-5%; and / or Ln2O3: 0-5%; and / or ZrO2: 0-5%; and / or TiO2: 0-2%; and / or P2O5: 0-3%; and / or SnO2: 0-1%, wherein Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0007] (3) A glass product with a blackening layer, the composition of which includes SiO2, B2O3, BaO, ZnO, K2O, Na2O and Sb2O3, wherein the coefficient of thermal expansion of the glass product with the blackening layer is α. 0-300℃ 45×

[0008] 10 -7 / K~75×10 -7 / K, for glass products with a blackened layer thickness of less than 10mm, the light transmittance of the blackened layer portion in the 400-900nm range is ≤3.0%, and the light transmittance of the transparent portion in the 400-900nm range of glass products with a blackened layer thickness of less than 10mm is ≥90.0%.

[0009] (4) The glass article with a blackened layer according to (3) comprises, by weight percentage: SiO2: 51-68%; and / or B2O3: 6-19%; and / or BaO: 6-19%; and / or ZnO: 1-10%; and / or K2O: 0.5-10%; and / or Na2O: greater than 0 but less than or equal to 8%; and / or Bi2O3: 0-4%; and / or Sb2O3: greater than 0 but less than or equal to 2%; and / or Al2O3: 0-8%; and / or SrO: 0-5%; and / or MgO: 0-5%; and / or CaO: 0-5%; and / or Li2O: 0-5%; and / or Ln2O3: 0-5%; and / or ZrO2: 0-5%; and / or TiO2: 0-2%; and / or P2O5: 0-3%; and / or SnO2: 0-1%, wherein the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0010] (5) A glass article having a blackening layer according to any one of (1) to (4), wherein the composition, expressed as a weight percentage, satisfies one or more of the following 12 conditions:

[0011] 1) The SiO2 / BaO ratio is 3.5 to 10.0, preferably 4.0 to 7.0, and more preferably 4.2 to 5.5;

[0012] 2) The ratio of (SiO2+K2O) / (B2O3+Al2O3) is 2.0 to 10.0, preferably 2.5 to 8.0, more preferably 3.0 to 7.0, and even more preferably 3.5 to 5.0.

[0013] 3) The ratio of Na2O / (Na2O+K2O) is 0.05 to 0.8, preferably 0.1 to 0.6, more preferably 0.1 to 0.5, and even more preferably 0.15 to 0.35;

[0014] 4) The BaO / Na2O ratio is 2.0 to 20.0, preferably 3.0 to 15.0, more preferably 4.0 to 10.0, and even more preferably 5.0 to 7.5;

[0015] 5) The BaO / ZnO ratio is 1.0 to 10.0, preferably 1.2 to 8.0, more preferably 1.5 to 5.0, and even more preferably 1.8 to 3.0;

[0016] 6) The ZnO / (Na2O+K2O) ratio is 0.1 to 5.0, preferably 0.2 to 3.0, more preferably 0.4 to 2.0, and even more preferably 0.5 to 1.0;

[0017] 7) The ratio of (ZnO+BaO) / (SiO2+Na2O) is 0.1 to 0.5, preferably 0.15 to 0.45, more preferably 0.2 to 0.4, and even more preferably 0.23 to 0.37.

[0018] 8) The ZnO / (RO+Ln2O3) ratio is 0.05 to 1.0, preferably 0.1 to 0.8, more preferably 0.2 to 0.7, and even more preferably 0.25 to 0.6;

[0019] 9) The ratio of Ln2O3 / BaO is 0.5 or less, preferably 0.3 or less, more preferably 0.2 or less, and even more preferably 0.1 or less;

[0020] 10) The ratio of 10×Bi₂O₃ / BaO is 0.05 to 4.0, preferably 0.1 to 3.0, more preferably 0.2 to 2.0, and even more preferably 0.25 to 1.0;

[0021] 11) The Bi2O3 / Sb2O3 ratio is 0.1 to 10.0, preferably 0.5 to 8.0, more preferably 1.0 to 6.0, and even more preferably 1.0 to 4.0;

[0022] 12. The ratio of (CaO+TiO2) / B2O3 is 0.8 or less, preferably 0.6 or less, more preferably 0.5 or less, and even more preferably 0.2 or less.

[0023] The Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3, and RO is the total content of BaO, SrO, CaO, and MgO.

[0024] (6) A glass article having a blackened layer according to any one of (1) to (4), wherein the components are expressed as weight percentages, wherein: SiO2: 52-65%, preferably SiO2: 56-61%; and / or B2O3: 8-18%, preferably B2O3: 10-15%; and / or BaO: 8-17%, preferably BaO: 10-15%; and / or ZnO: 2-8%, preferably ZnO: 3-7%; and / or K2O: 1-8%, preferably K2O: 3-7%; and / or Na2O: 0.5-7%, preferably Na2O: 1-5%; and / or Sb2O3: 0.05-1.5%, preferably Sb2O3: 0.1-1%; and / or Bi2O3: 0.05-3%, preferably Bi2O3: 0.1-1%; and / or Al2O3: 1-6% The preferred components are Al2O3: 2-5%; and / or SrO: 0-3%, preferably SrO: 0-1%; and / or MgO: 0-3%, preferably MgO: 0-1%; and / or CaO: 0-3%, preferably CaO: 0-1%; and / or Li2O: 0-3%, preferably Li2O: 0-1%; and / or Ln2O3: 0-3%, preferably Ln2O3: 0-2%; and / or ZrO2: 0-3%, preferably ZrO2: 0-2%; and / or TiO2: 0-1%, preferably TiO2: 0-0.5%; and / or P2O5: 0-1%, preferably P2O5: 0-0.5%; and / or SnO2: 0-0.5%, preferably SnO2: 0-0.2%, wherein the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0025] (7) The glass article having a blackened layer according to any one of (1) to (4) further contains, by weight percentage: As2O3: 0 to 2%, preferably As2O3: 0 to 1%, more preferably As2O3: 0 to 0.5%, and even more preferably does not contain As2O3.

[0026] (8) A glass article with a blackening layer according to any one of (1) to (4), wherein the composition does not contain MgO; and / or does not contain SrO; and / or does not contain CaO; and / or does not contain Li2O; and / or does not contain TiO2; and / or does not contain ZrO2; and / or does not contain P2O5; and / or does not contain Ln2O3; and / or does not contain SnO2; and / or does not contain PbO, wherein Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0027] (9) A glass article with a blackened layer according to any one of (1) to (4), wherein the density ρ of the glass article with a blackened layer is 3.00 g / cm³. 3 The preferred value is 2.90 g / cm³. 3 The following is a preferred value: 2.80 g / cm³3 The following is a further preferred value: 2.70 g / cm³ 3 The following; and / or the coefficient of thermal expansion α 0-300℃ 45×10 -7 / K~75×10 -7 / K, preferably 50×10 -7 / K~70×10 -7 / K, more preferably 55×10 -7 / K~65×10 -7 / K, further preferably 57×10 -7 / K~62×10 -7 / K; and / or acid resistance stability D A It is classified as Class 2 or above, preferably Class 1; and / or water resistance stability D W The weather resistance (CR) is classified as Class 2 or more, preferably Class 1; and / or the weather resistance (CR) is classified as Class 2 or more, preferably Class 1; and / or the transition temperature (T) is... g The upper limit of the crystallization temperature is 570–610°C, preferably 575–605°C, more preferably 580–600°C, and even more preferably 580–595°C; and / or the upper limit of the crystallization temperature T. max The temperature is below 1050°C, preferably below 1000°C, more preferably below 950°C, and even more preferably below 900°C.

[0028] (10) For a glass article with a blackened layer according to any one of (1) to (4), the light transmittance of the blackened layer portion of the glass article with a thickness of 10 mm or less is ≤3.0% in the 400-900 nm range, preferably ≤2.0% in the 400-900 nm range, more preferably ≤1.0% in the 400-900 nm range, and even more preferably ≤0.5% in the 400-900 nm range; and the light transmittance of the transparent portion of the glass article with a blackened layer with a thickness of 10 mm or less is ≥90.0% in the 400-900 nm range, preferably ≥90.5% in the 400-900 nm range, more preferably ≥91.0% in the 400-900 nm range, and even more preferably ≥91.5% in the 400-900 nm range.

[0029] (11) The glass article with a blackened layer according to (10) has a thickness of 1 to 8 mm, preferably 2 to 6 mm, and more preferably 3 to 5 mm.

[0030] (12) The matrix glass, whose composition is expressed as a percentage by weight, contains: SiO2: 51-68%; B2O3: 6-19%; BaO: 6-19%; ZnO: 1-10%; K2O: 0.5-10%; Na2O: greater than 0 but less than or equal to 8%; Sb2O3: greater than 0 but less than or equal to 2%, of which SiO2 / BaO is 3.0-11.0.

[0031] (13) The matrix glass according to (12) further comprises, by weight percentage: Bi2O3: 0-4%; and / or Al2O3: 0-8%; and / or SrO: 0-5%; and / or MgO: 0-5%; and / or CaO: 0-5%; and / or Li2O: 0-5%; and / or Ln2O3: 0-5%; and / or ZrO2: 0-5%; and / or TiO2: 0-2%; and / or P2O5: 0-3%; and / or SnO2: 0-1%, wherein the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0032] (14) The matrix glass according to (12) or (13) has components expressed as weight percentages that satisfy one or more of the following 12 conditions:

[0033] 1) The SiO2 / BaO ratio is 3.5 to 10.0, preferably 4.0 to 7.0, and more preferably 4.2 to 5.5;

[0034] 2) The ratio of (SiO2+K2O) / (B2O3+Al2O3) is 2.0 to 10.0, preferably 2.5 to 8.0, more preferably 3.0 to 7.0, and even more preferably 3.5 to 5.0.

[0035] 3) The ratio of Na2O / (Na2O+K2O) is 0.05 to 0.8, preferably 0.1 to 0.6, more preferably 0.1 to 0.5, and even more preferably 0.15 to 0.35;

[0036] 4) The BaO / Na2O ratio is 2.0 to 20.0, preferably 3.0 to 15.0, more preferably 4.0 to 10.0, and even more preferably 5.0 to 7.5;

[0037] 5) The BaO / ZnO ratio is 1.0 to 10.0, preferably 1.2 to 8.0, more preferably 1.5 to 5.0, and even more preferably 1.8 to 3.0;

[0038] 6) The ZnO / (Na2O+K2O) ratio is 0.1 to 5.0, preferably 0.2 to 3.0, more preferably 0.4 to 2.0, and even more preferably 0.5 to 1.0;

[0039] 7) The ratio of (ZnO+BaO) / (SiO2+Na2O) is 0.1 to 0.5, preferably 0.15 to 0.45, more preferably 0.2 to 0.4, and even more preferably 0.23 to 0.37.

[0040] 8) The ZnO / (RO+Ln2O3) ratio is 0.05 to 1.0, preferably 0.1 to 0.8, more preferably 0.2 to 0.7, and even more preferably 0.25 to 0.6;

[0041] 9) The ratio of Ln2O3 / BaO is 0.5 or less, preferably 0.3 or less, more preferably 0.2 or less, and even more preferably 0.1 or less;

[0042] 10) The ratio of 10×Bi₂O₃ / BaO is 0.05 to 4.0, preferably 0.1 to 3.0, more preferably 0.2 to 2.0, and even more preferably 0.25 to 1.0;

[0043] 11) The Bi2O3 / Sb2O3 ratio is 0.1 to 10.0, preferably 0.5 to 8.0, more preferably 1.0 to 6.0, and even more preferably 1.0 to 4.0;

[0044] 12. The ratio of (CaO+TiO2) / B2O3 is 0.8 or less, preferably 0.6 or less, more preferably 0.5 or less, and even more preferably 0.2 or less.

[0045] The Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3, and RO is the total content of BaO, SrO, CaO, and MgO.

[0046] (15) The matrix glass according to (12) or (13), wherein the components are expressed in weight percentages, wherein: SiO2: 52-65%, preferably SiO2: 56-61%; and / or B2O3: 8-18%, preferably B2O3: 10-15%; and / or BaO: 8-17%, preferably BaO: 10-15%; and / or ZnO: 2-8%, preferably ZnO: 3-7%; and / or K2O: 1-8%, preferably K2O: 3-7%; and / or Na2O: 0.5-7%, preferably Na2O: 1-5%; and / or Sb2O3: 0.05-1.5%, preferably Sb2O3: 0.1-1%; and / or Bi2O3: 0.05-3%, preferably Bi2O3: 0.1-1%; and / or Al2O3: 1-6%, preferably... The following are selected: Al2O3: 2-5%; and / or SrO: 0-3%, preferably SrO: 0-1%; and / or MgO: 0-3%, preferably MgO: 0-1%; and / or CaO: 0-3%, preferably CaO: 0-1%; and / or Li2O: 0-3%, preferably Li2O: 0-1%; and / or Ln2O3: 0-3%, preferably Ln2O3: 0-2%; and / or ZrO2: 0-3%, preferably ZrO2: 0-2%; and / or TiO2: 0-1%, preferably TiO2: 0-0.5%; and / or P2O5: 0-1%, preferably P2O5: 0-0.5%; and / or SnO2: 0-0.5%, preferably SnO2: 0-0.2%, wherein the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0047] (16) The matrix glass according to (12) or (13) further contains, by weight percentage: As2O3: 0-2%, preferably As2O3: 0-1%, more preferably As2O3: 0-0.5%, and even more preferably does not contain As2O3.

[0048] (17) The matrix glass according to (12) or (13) is free from MgO; and / or free from SrO; and / or free from CaO; and / or free from Li2O; and / or free from TiO2; and / or free from ZrO2; and / or free from P2O5; and / or free from Ln2O3; and / or free from SnO2; and / or free from PbO, wherein Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0049] (18) The refractive index n of the matrix glass according to (12) or (13) dThe value is 1.50 to 1.56, preferably 1.51 to 1.55, more preferably 1.515 to 1.54; and / or the Abbe number v d The density is 60-66, preferably 61-65, more preferably 62-64; and / or the density ρ is 3.00 g / cm³. 3 The preferred value is 2.90 g / cm³. 3 The following is a preferred value: 2.80 g / cm³ 3 The following is a further preferred value: 2.70 g / cm³ 3 The following; and / or the coefficient of thermal expansion α 0-300℃ 45×10 -7 / K~75×10 -7 / K, preferably 50×10 -7 / K~70×10 -7 / K, more preferably 55×10 -7 / K~65×10 -7 / K, further preferably 57×10 -7 / K~62×10 -7 / K; and / or acid resistance stability D A It is classified as Class 2 or above, preferably Class 1; and / or water resistance stability D W The weather resistance (CR) is classified as Class 2 or more, preferably Class 1; and / or the weather resistance (CR) is classified as Class 2 or more, preferably Class 1; and / or the transition temperature (T) is... g The upper limit of the crystallization temperature is 570–610°C, preferably 575–605°C, more preferably 580–600°C, and even more preferably 580–595°C; and / or the upper limit of the crystallization temperature T. max The temperature is below 1050°C, preferably below 1000°C, more preferably below 950°C, and even more preferably below 900°C.

[0050] (19) The light transmittance τ of the matrix glass according to (12) or (13) before blackening treatment. 前400-900nm ≥90.0%, preferred light transmittance τ 前400-900nm ≥90.5%, more preferably light transmittance τ 前400-900nm ≥91.0%, further optimized light transmittance τ 前400-900nm ≥91.5%; and / or light transmittance τ after blackening treatment. 后400-900nm ≤3.0%, preferred light transmittance τ 后400-900nm ≤2.0%, more preferably light transmittance τ 后400-900nm ≤1.0%, further optimize light transmittance τ 后400-900nm ≤0.5%.

[0051] (20) An optical element made of a glass article having a blackening layer as described in any of (1) to (11), or made of a matrix glass as described in any of (12) to (19).

[0052] (21) An optical instrument comprising a glass article having a blackening layer as described in any of (1) to (11), and / or a matrix glass as described in any of (12) to (19), and / or an optical element as described in (20).

[0053] (22) A method for manufacturing a glass article having a blackened layer, the method comprising the following steps: 1) forming a matrix glass; 2) processing a glass molded body; 3) blackening treatment; 4) shaping treatment.

[0054] (23) The manufacturing method of the glass article with a blackened layer according to (22) includes processing the glass body by direct dripping, grinding, polishing, and / or molding to form a glass body with a certain shape from the matrix glass, the glass body having a 2D, 2.5D or 3D structure.

[0055] (24) According to the manufacturing method of the glass article with a blackened layer described in (22), the blackening treatment involves placing the glass molded body in a reducing atmosphere at a certain temperature for a certain period of time, preferably hydrogen or carbon monoxide, more preferably hydrogen; the preferred temperature is T. g Below -10℃, a more preferred temperature is T. g -10℃~T g -200℃, with a further preferred temperature of T g -20℃~T g -100℃, with an even more preferred temperature of T g -20℃~T g -60℃, with a further preferred temperature of T g -30℃~T g -50℃; the preferred blackening treatment time is 50 to 1000 hours, more preferably 100 to 800 hours, further preferably 200 to 700 hours, and even more preferably 300 to 600 hours.

[0056] (25) According to the manufacturing method of glass articles with blackening layer described in (22), the shaping process is to process a specific area of ​​the blackened glass molded body, remove the blackening layer of the specific area, so that the specific area of ​​the glass is transparent, while other areas have blackening layer.

[0057] The beneficial effects of this invention are: through reasonable component design, the glass articles with a blackened layer of this invention have a suitable coefficient of thermal expansion. In some embodiments, the coefficient of thermal expansion of the glass articles with a blackened layer obtained by this invention can match that of gallium arsenide materials. Detailed Implementation

[0058] The embodiments 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 present invention's objectives. Furthermore, while there are instances of appropriate omissions in the repeated descriptions, this does not limit the scope of the invention. In the following text, the matrix glass of the present invention will sometimes be simply referred to as glass.

[0059] [Matrix Glass]

[0060] The component ranges of the matrix glass of the present invention are described below. In the present invention, unless otherwise specified, the content and total content of each component are expressed as a weight percentage (wt%), that is, the weight percentage of the content and total content 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, complex salts, and hydroxides used as raw materials for the matrix glass of the present invention decompose and transform into oxides upon melting, the total amount of such oxides is taken as 100%.

[0061] 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.

[0062] <Essential and Optional Components>

[0063] SiO2 forms the framework of glass, playing a crucial role in maintaining its chemical stability and improving its resistance to devitrification. In this invention, the above-mentioned effects are achieved by containing at least 51% SiO2, preferably at least 52%, and more preferably at least 56%. If the SiO2 content exceeds 68%, the glass meltability decreases, vitrification becomes difficult, and internal quality problems such as stone formation are easily encountered. Simultaneously, the glass transition temperature increases. Therefore, the upper limit for the SiO2 content is 68%, preferably 65%, and more preferably 61%.

[0064] B2O3 can improve the melt flow properties and devitrification resistance of glass, but when its content is too high, the chemical stability of the glass decreases and it has an adverse effect on the coefficient of thermal expansion. Therefore, the content of B2O3 in this invention is 6-19%, preferably 8-18%, and more preferably 10-15%.

[0065] Al2O3 can improve the chemical stability, mechanical strength, and weather resistance of glass. However, if its content is too high, the meltability of the glass decreases and its resistance to crystallization deteriorates. Therefore, the content of Al2O3 is 0–8%, preferably 1–6%, and more preferably 2–5%.

[0066] BaO can increase the refractive index of glass, improve its coefficient of thermal expansion and high-temperature viscosity. However, if its content is too high, the chemical stability of the glass deteriorates. Therefore, the BaO content is limited to 6-19%, preferably 8-17%, and more preferably 10-15%.

[0067] In some embodiments, controlling the ratio of SiO2 content to BaO content (SiO2 / BaO) within the range of 3.0 to 11.0 is beneficial for the glass to obtain excellent thermal expansion coefficient and chemical stability, and optimizes the glass density. Therefore, a SiO2 / BaO ratio of 3.0 to 11.0 is preferred, a SiO2 / BaO ratio of 3.5 to 10.0 is more preferred, a SiO2 / BaO ratio of 4.0 to 7.0 is even more preferred, and a SiO2 / BaO ratio of 4.2 to 5.5 is even more preferred.

[0068] SrO can adjust the refractive index and Abbe number of glass, but if its content is too high, the chemical stability of the glass decreases, and the cost of the glass also increases rapidly. Therefore, the content of SrO is limited to 0-5%, preferably 0-3%, and more preferably 0-1%. In some embodiments, it is even more preferable that the glass does not contain SrO.

[0069] CaO helps to improve the refractive index and hardness of glass and optimize its abrasion resistance. However, if the CaO content is too high, it will lead to a decrease in the glass's resistance to crystallization. Therefore, the CaO content is 0-5%, preferably 0-3%, and more preferably 0-1%. In some embodiments, it is even more preferable that the glass does not contain CaO.

[0070] MgO can reduce the relative partial dispersion of glass, but if the MgO content is too high, the refractive index of the glass is difficult to meet the design requirements, and the glass's anti-crystallization performance and stability decrease. Therefore, the MgO content is limited to 0-5%, preferably 0-3%, and more preferably 0-1%. In some embodiments, it is further preferred that the glass does not contain MgO.

[0071] K2O improves the thermal stability and melt permeability of glass, and this invention achieves these effects by containing more than 0.5% K2O. However, if the K2O content exceeds 10%, the glass's resistance to devitrification and chemical stability decrease. Therefore, the K2O content in this invention is 0.5% to 10%, preferably 1% to 8%, and more preferably 3% to 7%.

[0072] In some embodiments, controlling the ratio of the total content of SiO2 and K2O (SiO2+K2O) to the total content of B2O3 and Al2O3 (B2O3+Al2O3), (SiO2+K2O) / (B2O3+Al2O3), within the range of 2.0 to 10.0 is beneficial for improving the glass's resistance to crystallization, preventing an increase in glass density, and optimizing the glass's blackening properties. Therefore, it is preferable that (SiO2+K2O) / (B2O3+Al2O3) is 2.0 to 10.0, more preferably (SiO2+K2O) / (B2O3+Al2O3) is 2.5 to 8.0, further preferably (SiO2+K2O) / (B2O3+Al2O3) is 3.0 to 7.0, and even more preferably (SiO2+K2O) / (B2O3+Al2O3) is 3.5 to 5.0.

[0073] Na₂O improves the meltability of glass, thus enhancing the glass melting process. However, excessive Na₂O content reduces the chemical stability and weather resistance of the glass. Therefore, the Na₂O content is greater than 0 but less than or equal to 8%, preferably 0.5–7%, and more preferably 1–5%.

[0074] In some embodiments, controlling the Na2O / (Na2O+K2O) ratio within the range of 0.05 to 0.8 is beneficial for the glass to achieve excellent thermal expansion coefficient while optimizing its weather resistance. Therefore, a Na2O / (Na2O+K2O) ratio of 0.05 to 0.8 is preferred, a Na2O / (Na2O+K2O) ratio of 0.1 to 0.6 is more preferred, a Na2O / (Na2O+K2O) ratio of 0.1 to 0.5 is even more preferred, and a Na2O / (Na2O+K2O) ratio of 0.15 to 0.35 is even more preferred.

[0075] In some embodiments, controlling the ratio of BaO content to Na2O content (BaO / Na2O) within the range of 2.0 to 20.0 is beneficial for improving the chemical stability and weather resistance of the glass and optimizing the glass transition temperature. Therefore, a BaO / Na2O ratio of 2.0 to 20.0 is preferred, more preferably 3.0 to 15.0, even more preferably 4.0 to 10.0, and still more preferably 5.0 to 7.5.

[0076] ZnO can improve the melting properties of glass, lower its transition temperature and high-temperature viscosity, and facilitate the elimination of bubbles within the glass; however, excessive ZnO content can reduce the glass's resistance to devitrification and its chemical stability. Therefore, the ZnO content is 1–10%, preferably 2–8%, and more preferably 3–7%.

[0077] In some embodiments, controlling the ratio of BaO content to ZnO content (BaO / ZnO) within the range of 1.0 to 10.0 can improve the light transmittance of the glass and prevent a decrease in the transition temperature. Therefore, a BaO / ZnO ratio of 1.0 to 10.0 is preferred, a BaO / ZnO ratio of 1.2 to 8.0 is more preferred, a BaO / ZnO ratio of 1.5 to 5.0 is even more preferred, and a BaO / ZnO ratio of 1.8 to 3.0 is still preferred.

[0078] In some embodiments, controlling the ratio of ZnO content to the total content of Na2O and K2O (Na2O+K2O), ZnO / (Na2O+K2O), within the range of 0.1 to 5.0, is beneficial for the glass to achieve both excellent thermal expansion coefficient and optimized light transmittance. Therefore, a ZnO / (Na2O+K2O) ratio of 0.1 to 5.0 is preferred, more preferably 0.2 to 3.0, further preferably 0.4 to 2.0, and even more preferably 0.5 to 1.0.

[0079] In some embodiments, controlling the ratio of the total content of ZnO and BaO (ZnO+BaO) to the total content of SiO2 and Na2O (SiO2+Na2O), i.e., (ZnO+BaO) / (SiO2+Na2O), within the range of 0.1 to 0.5, is beneficial for improving the blackening performance and bubble content of the glass, and reducing the density and coefficient of thermal expansion of the glass. Therefore, it is preferable that (ZnO+BaO) / (SiO2+Na2O) is 0.1 to 0.5, more preferably (ZnO+BaO) / (SiO2+Na2O) is 0.15 to 0.45, further preferably (ZnO+BaO) / (SiO2+Na2O) is 0.2 to 0.4, and even more preferably (ZnO+BaO) / (SiO2+Na2O) is 0.23 to 0.37.

[0080] Li₂O can lower the glass transition temperature, adjust the high-temperature viscosity of glass, and improve the melting properties of glass. However, a high Li₂O content is detrimental to the chemical stability and cost-effectiveness of the glass. Therefore, the Li₂O content in this invention is 5% or less, preferably 3% or less, and more preferably 1% or less. In some embodiments, it is further preferred that Li₂O is not present.

[0081] Ln2O3 (Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3) is a component that improves the refractive index and chemical stability of glass. By controlling the content of Ln2O3 to below 5%, the devitrification resistance of the glass can be prevented from decreasing. Preferably, the upper limit of the Ln2O3 content range is 3%, more preferably 2%. In some embodiments, it is further preferred that the glass does not contain Ln2O3.

[0082] In some embodiments, controlling the ratio of ZnO content to the total content of alkaline earth metal components RO (where RO is the total content of BaO, SrO, CaO, and MgO) and Ln2O3, ZnO / (RO+Ln2O3), within the range of 0.05 to 1.0, allows the glass of the present invention to achieve the desired refractive index while possessing excellent transition temperature. Therefore, it is preferable that ZnO / (RO+Ln2O3) is 0.05 to 1.0, more preferably 0.1 to 0.8, further preferably 0.2 to 0.7, and even more preferably 0.25 to 0.6.

[0083] In some embodiments, controlling the ratio of Ln2O3 content to BaO content (Ln2O3 / BaO) to be below 0.5 can improve the weather resistance of the glass and prevent the glass's anti-crystallization properties and transition temperature from deteriorating. Therefore, it is preferable that Ln2O3 / BaO is below 0.5, more preferably below 0.3, further preferably below 0.2, and even more preferably below 0.1.

[0084] ZrO2 can improve the refractive index and chemical stability of glass, reduce its coefficient of thermal expansion, and optimize its high-temperature viscosity. However, when the ZrO2 content is too high, the glass's devitrification resistance decreases, melting difficulty increases, melting temperature rises, and inclusions and light transmittance appear within the glass. Therefore, the ZrO2 content in this invention is 0–5%, preferably 0–3%, and more preferably 0–2%. In some embodiments, it is further preferred that the glass does not contain ZrO2.

[0085] Bi₂O₃ can increase the refractive index and partial dispersion ratio of glass, which is beneficial to improving the weather resistance of glass. In this invention, the presence of Bi₂O₃ also improves the blackening performance of the glass and reduces its coefficient of thermal expansion. However, if the Bi₂O₃ content is too high, the glass's resistance to crystallization decreases. Therefore, the Bi₂O₃ content is 0–4%, preferably 0.05–3%, and more preferably 0.1–1%.

[0086] In some embodiments, controlling the 10×Bi₂O₃ / BaO ratio within the range of 0.05 to 4.0 can optimize the blackening performance and coefficient of thermal expansion of the glass while achieving excellent weather resistance. Therefore, it is preferable that the 10×Bi₂O₃ / BaO ratio is 0.05 to 4.0, more preferably 0.1 to 3.0, even more preferably 0.2 to 2.0, and even more preferably 0.25 to 1.0.

[0087] In this invention, by containing more than 0 but less than or equal to 2% Sb₂O₃, the substrate glass achieves a low light transmittance after blackening treatment. Preferably, the Sb₂O₃ content is 0.05–1.5%, more preferably 0.1–1%.

[0088] In some embodiments, controlling the ratio of Bi2O3 content to Sb2O3 content (Bi2O3 / Sb2O3) within the range of 0.1 to 10.0 is beneficial for improving the blackening performance of the glass and preventing a deterioration in its anti-crystallization properties. Therefore, a Bi2O3 / Sb2O3 ratio of 0.1 to 10.0 is preferred, a Bi2O3 / Sb2O3 ratio of 0.5 to 8.0 is more preferred, a Bi2O3 / Sb2O3 ratio of 1.0 to 6.0 is even more preferred, and a Bi2O3 / Sb2O3 ratio of 1.0 to 4.0 is even more preferred.

[0089] TiO2 improves the refractive index and dispersion of glass. However, if the TiO2 content is too high, the tendency of the glass to crystallize increases, and the transition temperature rises. Therefore, the TiO2 content in this invention is 0-2%, preferably 0-1%, and more preferably 0-0.5%. In some embodiments, it is further preferred that the glass does not contain TiO2.

[0090] In some embodiments, controlling the total content of CaO and TiO2, specifically the ratio of CaO+TiO2 to B2O3 (CaO+TiO2) / B2O3, to be below 0.8, can prevent a decrease in the glass's resistance to crystallization and transmittance, and prevent the glass's coefficient of thermal expansion from failing to meet design requirements. Therefore, it is preferable that (CaO+TiO2) / B2O3 is below 0.8, more preferably below 0.6, further preferably below 0.5, and even more preferably below 0.2.

[0091] P2O5 is an optional component that can improve the devitrification resistance of glass, and in particular, by keeping the P2O5 content below 3%, it can suppress the decrease in the chemical stability of the glass. Therefore, the P2O5 content is limited to 3% or less, preferably 1% or less, and more preferably 0.5% or less. In some embodiments, it is further preferred that P2O5 is not present.

[0092] SnO2, as a clarifying agent, can improve the clarification effect of glass and increase the bubble content of the glass. The SnO2 content is 0-1%, preferably 0-0.5%, and more preferably 0-0.2%. In some embodiments, it is further preferred that the glass does not contain SnO2.

[0093] In some embodiments, As2O3 can achieve the effect of low light transmittance after the matrix glass is blackened. However, the use of As2O3 will cause serious environmental pollution. Therefore, its content is limited to less than 2%, preferably less than 1%, more preferably less than 0.5%, and even more preferably does not contain As2O3.

[0094] <Components that should not be present>

[0095] To achieve environmental friendliness, the matrix glass of the present invention preferably does not contain PbO.

[0096] The terms "not containing" and "0%" as used herein mean that the compound, molecule, or element was not intentionally added as a raw material to the matrix glass of this invention. However, as raw materials and / or equipment used in the production of matrix glass, there may be some unintentionally added impurities or components that may be present in small or trace amounts in the final matrix glass. Such cases are also within the scope of protection of this patent.

[0097] The properties of the matrix glass of the present invention will now be described.

[0098] <Refractive Index and Abbe Number>

[0099] The refractive index (n) of the matrix glass d ) and Abbe number (ν d Test according to the method specified in GB / T 7962.1-2010.

[0100] In some embodiments, the refractive index (n) of the matrix glass of the present invention d The lower limit is 1.50, the preferred lower limit is 1.51, and the more preferred lower limit is 1.515.

[0101] In some embodiments, the refractive index (n) of the matrix glass of the present invention d The upper limit of ) is 1.56, the preferred upper limit is 1.55, and the more preferred upper limit is 1.54.

[0102] In some embodiments, the Abbe number (ν) of the matrix glass of the present invention d The lower limit is 60, the preferred lower limit is 61, and the more preferred lower limit is 62.

[0103] In some embodiments, the Abbe number (ν) of the matrix glass of the present invention d The upper limit of ) is 66, the preferred upper limit is 65, and the more preferred upper limit is 64.

[0104] <Density>

[0105] The density (ρ) of the matrix glass was tested according to the method specified in GB / T7962.20-2010.

[0106] In some embodiments, the density (ρ) of the matrix glass of the present invention is 3.00 g / cm³. 3 The preferred value is 2.90 g / cm³. 3 The following is a preferred value: 2.80 g / cm³ 3 The following is a further preferred value: 2.70 g / cm³ 3 the following.

[0107] <Coefficient of thermal expansion>

[0108] The coefficient of thermal expansion of the matrix glass (α) 0-300℃ Data from 0 to 300℃ were tested according to the method specified in GB / T7962.16-2010.

[0109] In some embodiments, the thermal expansion coefficient (α) of the matrix glass of the present invention is... 0-300℃ ) is 45×10 -7 / K~75×10 -7 / K, preferably 50×10 -7 / K~70×10 -7 / K, more preferably 55×10 -7 / K~65×10 -7 / K, further preferably 57×10 -7 / K~62×10 -7 / K.

[0110] <Stability under water resistance>

[0111] Water resistance stability of matrix glass (D) W (Powder method) Tested according to the method specified in GB / T 17129.

[0112] In some embodiments, the water resistance stability (D) of the matrix glass of the present invention is... W There are two or more categories, with category 1 being preferred.

[0113] <Stability under acid conditions>

[0114] Acid resistance stability of matrix glass (D) A (Powder method) Tested according to the method specified in GB / T 17129.

[0115] In some embodiments, the acid resistance stability (D) of the matrix glass of the present invention is... A There are two or more categories, with category 1 being preferred.

[0116] <Weather resistance>

[0117] The weather resistance (CR) test method for matrix glass is as follows: The sample is placed in a test chamber with a relative humidity of 90% saturated water vapor, and the temperature is alternately cyclical at 40–50℃ every 1 hour, for 15 cycles. Weather resistance is classified according to the change in turbidity before and after the sample placement. The weather resistance classification is shown in Table 1.

[0118] Table 1.

[0119]

[0120] In some embodiments, the weather resistance (CR) of the matrix glass of the present invention is Class 2 or above, preferably Class 1.

[0121] <Transition Temperature>

[0122] Transition temperature of matrix glass (T) g The test shall be conducted in accordance with the method specified in GB / T7962.16-2010.

[0123] In some embodiments, the transition temperature (T) of the matrix glass of the present invention is... g The temperature is 570–610℃, preferably 575–605℃, more preferably 580–600℃, and even more preferably 580–595℃.

[0124] <Upper limit of crystallization temperature>

[0125] Upper limit of crystallization temperature (T) max The test method is as follows: 10×10×150mm 3 A glass sample is placed in a platinum crucible and then placed in a temperature gradient furnace at 900–1200°C for 4 hours. Afterward, the crucible is removed from the furnace and allowed to cool naturally. The glass surface and any crystals within the glass are immediately observed. The lowest temperature within the set temperature range corresponding to the area where no crystals were found is taken as the "upper limit of crystallization temperature." It should be noted that this test method is only valid for crystallization temperatures between 900 and 1200°C. If no crystals are found on the entire surface and inside the sample after holding at this temperature, the sample's upper limit of crystallization temperature can be considered to be below 900°C.

[0126] Glasses with lower upper crystallization temperatures have a reduced risk of crystallization even when molten glass flows out at lower temperatures. This reduces the risk of devitrification during glass formation from the molten state, thus minimizing the impact on the optical properties of optical components using glass. Furthermore, lower crystallization temperatures allow for lower glass forming temperatures, reducing energy consumption during glass forming and lowering manufacturing costs.

[0127] The matrix glass of this invention exhibits excellent crystallization stability and has a low upper limit of crystallization temperature (T). max In some embodiments, the upper limit of the crystallization temperature (T) of the matrix glass of the present invention is... max The temperature is below 1050°C, preferably below 1000°C, more preferably below 950°C, and even more preferably below 900°C.

[0128] <Light transmittance>

[0129] The light transmittance of the glass was tested according to the method specified in GB / T7962.12-2010 for a 3mm thick sample.

[0130] In some embodiments, the light transmittance (τ) of the matrix glass before blackening treatment according to the present invention is... 前400-900nm Light transmittance ≥ 90.0%, preferably light transmittance (τ) 前400-900nm Light transmittance ≥ 90.5%, more preferably light transmittance (τ) 前400-900nm )≥91.0%, further optimized light transmittance (τ) 前400-900nm ≥91.5%.

[0131] The matrix glass of this invention was blackened in a hydrogen atmosphere for 400 hours at a temperature of T. g -30℃. In some embodiments, the light transmittance (τ) of the matrix glass after blackening treatment according to the present invention is... 后400-900nm Light transmittance ≤ 3.0%, preferably light transmittance (τ) 后400-900nm Light transmittance ≤ 2.0%, more preferably light transmittance (τ) 后400-900nm )≤1.0%, further optimize light transmittance (τ) 后400-900nm ≤0.5%.

[0132] [Manufacturing method of matrix glass]

[0133] The manufacturing method of the matrix glass of this invention is as follows: The glass of this invention is produced using conventional raw materials and processes, including but not limited to using oxides, hydroxides, complex salts (such as carbonates, nitrates, sulfates, etc.), boric acid, etc. as raw materials. After the raw materials are prepared according to conventional methods, the prepared furnace charge is put into a melting furnace (such as a platinum or platinum alloy crucible) at 1200-1600℃ for melting. After clarification and homogenization, a homogeneous molten glass without bubbles and 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.

[0134] [Glass products with a blackened layer and their manufacturing method]

[0135] The glass article with a blackened layer described in this invention is a transparent glass with a blackened layer, and the glass article with a blackened layer can be 2D, 2.5D, or 3D in construction. The 2.5D or 3D construction described herein refers to a glass article with a blackened layer having a non-planar construction. "Non-planar construction" as used herein means that in a 2.5D or 3D shape, at least a portion of the glass article with a blackened layer extends outward or along an angle with the plane defined by the original, layout configuration of the 2D matrix glass. The 2.5D or 3D glass article with a blackened layer formed from the matrix glass may have one or more protruding or curved portions. The glass article with a blackened layer of this invention can have any reasonably useful shape and thickness.

[0136] The present invention provides a method for manufacturing glass articles with a blackened layer, comprising processing a substrate glass into a glass mold, a blackening treatment, and a shaping treatment. The glass mold processing can be performed using methods such as direct drip forming, grinding, polishing, or molding to form a glass mold with a specific shape, wherein the glass mold has a 2D, 2.5D, or 3D structure. The blackening treatment forms a blackened layer on the surface of the glass mold by physical or chemical methods. In some embodiments, the blackening treatment involves placing the glass mold in a reducing atmosphere at a certain temperature for a certain period of time. Preferably, the reducing atmosphere is hydrogen (H2) or carbon monoxide (CO), more preferably hydrogen (H2); the preferred temperature is T. g Below -10℃, a more preferred temperature is T. g -10℃~T g -200℃, with a further preferred temperature of T g -20℃~T g -100℃, with an even more preferred temperature of T g -20℃~T g -60℃, with a further preferred temperature of T g -30℃~T g-50℃; the preferred blackening treatment time is 50–1000 hours, more preferably 100–800 hours, further preferably 200–700 hours, and even more preferably 300–600 hours. The shaping process involves processing a specific area of ​​the blackened glass molded body to remove the blackened layer from that area, making that specific area transparent while other areas retain the blackened layer, thus producing a glass product with a blackened layer. The size and location of the specific area can be determined according to actual needs.

[0137] The glass products with a blackened layer obtained by this invention have the same component content as the matrix glass, and the glass products with a blackened layer obtained by this invention possess the excellent properties of the matrix glass.

[0138] In some embodiments, the density (ρ) of the glass article having a blackened layer according to the present invention is 3.00 g / cm³. 3 The preferred value is 2.90 g / cm³. 3 The following is a preferred value: 2.80 g / cm³ 3 The following is a further preferred value: 2.70 g / cm³ 3 Below. In some embodiments, the coefficient of thermal expansion (α) of the glass article having a blackening layer according to the present invention is... 0-300℃ ) is 45×10 -7 / K~75×10 -7 / K, preferably 50×10 -7 / K~70×10 -7 / K, more preferably 55×10 -7 / K~65×10 -7 / K, further preferably 57×10 -7 / K~62×10 -7 / K. In some embodiments, the present invention provides water resistance stability (D) of glass articles with a blackened layer. W The glass article of the present invention has two or more categories, preferably one category. In some embodiments, the glass article with the blackened layer exhibits improved acid resistance stability (D...). A The weather resistance (CR) of the glass article with the blackening layer of the present invention is of class 2 or more, preferably class 1. In some embodiments, the weather resistance (CR) of the glass article with the blackening layer of the present invention is of class 2 or more, preferably class 1. In some embodiments, the transition temperature (T) of the glass article with the blackening layer of the present invention is... g The crystallization temperature is 570–610℃, preferably 575–605℃, more preferably 580–600℃, and even more preferably 580–595℃. In some embodiments, the upper limit of the crystallization temperature (T) of the glass article having a blackening layer according to the present invention is... max The temperature is below 1050°C, preferably below 1000°C, more preferably below 950°C, and even more preferably below 900°C.

[0139] The light transmittance of the glass article with a blackened layer is tested according to the method specified in GB / T7962.12-2010. In some embodiments, the light transmittance of the blackened layer portion of the glass article with a blackened layer thickness of 10 mm or less in the 400-900 nm range is ≤3.0%, preferably ≤2.0%, more preferably ≤1.0%, and even more preferably ≤0.5%. In some embodiments, the light transmittance of the transparent portion of the glass article with a blackened layer thickness of 10 mm or less in the 400-900 nm range is ≥90.0%, preferably ≥90.5%, more preferably ≥91.0%, and even more preferably ≥91.5%. Preferably, the above thickness is 1-8 mm, more preferably 2-6 mm, and even more preferably 3-5 mm.

[0140] In some embodiments, the glass article with the blackening layer may be anti-halo stepped glass.

[0141] The manufacturing method of anti-halo stepped glass mainly includes processing the substrate glass into a glass mold, blackening treatment, and shaping treatment. The glass molding process can use methods such as direct drip molding, grinding, polishing, and / or molding to form a stepped glass mold. The blackening treatment forms a black layer on the surface of the glass mold by physical or chemical methods. In some embodiments, the blackening treatment involves placing the glass mold in a reducing atmosphere at a certain temperature for a certain period of time. Preferably, the reducing atmosphere is hydrogen (H2) or carbon monoxide (CO), more preferably hydrogen (H2); the preferred temperature is T. g Below -10℃, a more preferred temperature is T. g -10℃~T g -200℃, with a further preferred temperature of T g -20℃~T g -100℃, with an even more preferred temperature of T g -20℃~T g -60℃, with a further preferred temperature of T g -30℃~T g-50℃; the preferred blackening treatment time is 50-1000 hours, more preferably 100-800 hours, further preferably 200-700 hours, and even more preferably 300-600 hours. The shaping process involves processing the blackened layers on both the upper and lower surfaces of the blackened glass molded body, removing the blackened layers from both surfaces, and simultaneously polishing the blackened layers on the inclined surfaces, stepped surfaces, and cylindrical surfaces, and rounding some of the top corners to obtain anti-halo stepped glass.

[0142] The anti-halo stepped glass obtained by this invention has the same component content as the matrix glass, and the anti-halo stepped glass obtained by this invention possesses the excellent properties of the matrix glass.

[0143] In some embodiments, the density (ρ) of the anti-halo stepped glass of the present invention is 3.00 g / cm³. 3 The preferred value is 2.90 g / cm³. 3 The following is a preferred value: 2.80 g / cm³ 3 The following is a further preferred value: 2.70 g / cm³ 3 Below. In some embodiments, the coefficient of thermal expansion (α) of the anti-halo stepped glass of the present invention is... 0-300℃ ) is 45×10 -7 / K~75×10 -7 / K, preferably 50×10 -7 / K~70×10 -7 / K, more preferably 55×10 -7 / K~65×10 -7 / K, further preferably 57×10 -7 / K~62×10 -7 / K. In some embodiments, the water resistance stability (D) of the anti-halo stepped glass of the present invention is... W The glass is classified into two or more categories, preferably one category. In some embodiments, the anti-halo stepped glass of the present invention exhibits acid resistance stability (D...). A The weather resistance (CR) of the anti-halo stepped glass of the present invention is classified as Class 2 or more, preferably Class 1. In some embodiments, the weather resistance (CR) of the anti-halo stepped glass of the present invention is Class 2 or more, preferably Class 1. In some embodiments, the transition temperature (T) of the anti-halo stepped glass of the present invention is... g The crystallization temperature is 570–610℃, preferably 575–605℃, more preferably 580–600℃, and even more preferably 580–595℃. In some embodiments, the upper limit of the crystallization temperature (T) of the anti-halo stepped glass of the present invention is... max The temperature is below 1050°C, preferably below 1000°C, more preferably below 950°C, and even more preferably below 900°C.

[0144] In some embodiments, the light transmittance of the blackened layer portion of the anti-halo stepped glass with a thickness of 10 mm or less in the 400-900 nm range is ≤3.0%, preferably ≤2.0%, more preferably ≤1.0%, and even more preferably ≤0.5%. In some embodiments, the light transmittance of the transparent portion of the anti-halo stepped glass with a thickness of 10 mm or less in the 400-900 nm range is ≥90.0%, preferably ≥90.5%, more preferably ≥91.0%, and even more preferably ≥91.5%. Preferably, the thickness is 1-8 mm, more preferably 2-6 mm, and even more preferably 3-5 mm.

[0145] [Glass preforms and optical components]

[0146] Glass preforms can be manufactured from the substrate glass using methods such as direct drop forming, grinding, or hot pressing. Specifically, glass preforms can be manufactured by directly and precisely drop-forming molten substrate glass into precision glass preforms, or by machining such as grinding and polishing, or by hot pressing a preform made from the substrate glass for molding and then grinding it. It should be noted that the methods for preparing glass preforms are not limited to the methods described above.

[0147] As described above, the matrix glass of the present invention is useful for various optical elements and optical designs, and it is particularly preferred to form a preform from the matrix glass of the present invention, using the preform for hot pressing, precision stamping, etc., to manufacture optical elements such as lenses and prisms.

[0148] Both the glass preform and the optical element of the present invention are formed from the matrix glass described above. The glass preform of the present invention possesses the excellent properties of the matrix glass; the optical element of the present invention possesses the excellent properties of the matrix glass, and can provide various optical elements such as lenses and prisms with high optical value.

[0149] Examples of lenses include concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, plano-concave lenses, and so on, where the lens surface is spherical or aspherical.

[0150] [Optical Instruments]

[0151] The optical elements formed from the matrix glass of this invention, glass with a blackening layer, glass products with a blackening layer, and anti-halo stepped glass can be used to manufacture optical instruments such as low-light night vision devices, photographic equipment, video equipment, projection equipment, display equipment, vehicle-mounted equipment, and monitoring equipment.

[0152] Example

[0153] <Matrix Glass Examples>

[0154] To further illustrate and explain the technical solution of the present invention, the following non-limiting embodiments are provided.

[0155] This embodiment uses the above-described method for manufacturing matrix glass to obtain matrix glass with the compositions shown in Tables 2 to 4. Furthermore, the properties of each glass were measured using the testing method described in this invention, and the results are shown in Tables 2 to 4. The blackening performance test results of this embodiment are obtained by blackening the matrix glass in this embodiment in a hydrogen atmosphere for 400 hours at a blackening temperature of T. g -30℃, and the light transmittance after blackening is shown in Tables 2 to 4.

[0156] Table 2.

[0157]

[0158]

[0159] Table 3.

[0160]

[0161]

[0162] Table 4.

[0163]

[0164]

[0165]

[0166] <Examples of glass products with a blackened layer>

[0167] The glass obtained from the matrix glass in Example 24# was manufactured into a 3D glass molded body by grinding. The glass molded body was then placed in a hydrogen atmosphere at 560°C for 400 hours. The blackened layer of part of the glass molded body was then processed to expose the transparent glass inside. Finally, it was polished to obtain a glass product with a blackened layer.

[0168] <Anti-halo stepped glass example>

[0169] The glass obtained from Example 2# of the matrix glass was processed into a stepped glass body by grinding. The glass body was then placed in a hydrogen atmosphere at 566°C for 500 hours. The blackened layers on the top and bottom surfaces of the glass body were then processed to expose the transparent glass inside. At the same time, the blackened layers on the inclined surface, stepped surface and cylindrical surface were polished, and some of the top corners were rounded to obtain anti-halo stepped glass.

[0170] <Example of Glass Prefabricated Components>

[0171] The glass obtained from the matrix glass examples 10 to 20# is used to manufacture preforms of various lenses and prisms, such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses, by means of grinding, hot pressing, precision stamping, or other molding methods.

[0172] <Optical Component Examples>

[0173] Annealing these preforms obtained from the above glass preform examples reduces internal stress in the glass while fine-tuning the refractive index, so that optical properties such as the refractive index reach the desired values.

[0174] Next, the prefabricated parts are ground and polished to produce various lenses and prisms, such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses. Anti-reflective coatings can also be applied to the surface of the resulting optical elements.

[0175] <Examples of Optical Instruments>

[0176] The optical elements obtained from the above-described optical element embodiments can be used, through optical design, to form optical components or optical assemblies by using one or more optical elements. These components can be used in, for example, imaging devices, sensors, microscopes, medical technology, digital projection, communications, optical communication technology / information transmission, optics / lighting in the automotive field, lithography technology, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices that include such circuits and chips.

Claims

1. A glass product having a blackened layer, characterized in that, Its composition, expressed as a weight percentage, contains: SiO2: 51–68%; B2O3: 6–19%; BaO: 6–19%; ZnO: 1–10%; K2O: 0.5–10%; Na2O: greater than 0 but less than or equal to 4.8%; Sb2O3: greater than 0 but less than or equal to 2%, of which SiO2 / BaO is 3.0–11.0, 10×Bi2O3 / BaO is 0.05–4.0, Na2O / (Na2O+K2O) is 0.05–0.5, and it does not contain Li2O.

2. The glass article with a blackening layer according to claim 1, characterized in that, Its components, expressed as a weight percentage, also contain: Bi2O3: 0.05–4%; and / or Al2O3: 0–8%; and / or SrO: 0–5%; and / or MgO: 0–5%; and / or CaO: 0–5%; and / or Ln2O3: 0–5%; and / or ZrO2: 0–5%; and / or TiO2: 0–2%; and / or P2O5: 0–3%; and / or SnO2: 0–1%, wherein the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

3. A glass product having a blackened layer, characterized in that, Its composition includes SiO2, B2O3, BaO, ZnO, K2O, Na2O, and Sb2O3. Na2O content is greater than 0 but less than or equal to 4.8%. The ratio of 10×Bi2O3 / BaO is 0.05–4.0, and the ratio of Na2O / (Na2O+K2O) is 0.05–0.

5. It does not contain Li2O. The coefficient of thermal expansion α of the glass product with the blackening layer is... 0-300℃ 45×10 -7 / K~75×10 -7 / K, for glass products with a blackened layer thickness of less than 10mm, the light transmittance of the blackened layer portion in the 400-900nm range is ≤3.0%, and the light transmittance of the transparent portion in the 400-900nm range of glass products with a blackened layer thickness of less than 10mm is ≥90.0%.

4. The glass article with a blackened layer according to claim 3, characterized in that, Its composition, expressed as a weight percentage, contains: SiO2: 51-68%; and / or B2O3: 6-19%; and / or BaO: 6-19%; and / or ZnO: 1-10%; and / or K2O: 0.5-10%; and / or Bi2O3: 0.05-4%; and / or Sb2O3: greater than 0 but less than or equal to 2%; and / or Al2O3: 0-8%; and / or SrO: 0-5%; and / or MgO: 0-5%; and / or CaO: 0-5%; and / or Ln2O3: 0-5%; and / or ZrO2: 0-5%; and / or TiO2: 0-2%; and / or P2O5: 0-3%; and / or SnO2: 0-1%, wherein the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

5. The glass article having a blackened layer according to any one of claims 1 to 4, characterized in that, Its components are expressed as a weight percentage and satisfy one or more of the following 12 conditions: 1) The SiO2 / BaO ratio is 3.5–10.0; 2)(SiO2+K2O) / (B2O3+Al2O3) is 2.0~10.0; 3) The ratio of Na₂O / (Na₂O+K₂O) is 0.1–0.5; 4) The BaO / Na2O ratio is 2.0–20.0; 5) BaO / ZnO is 1.0~10.0; 6) ZnO / (Na2O+K2O) is 0.1~5.0; 7) (ZnO+BaO) / (SiO2+Na2O) is 0.1~0.5; 8) ZnO / (RO+Ln2O3) is 0.05~1.0; 9) The ratio of Ln₂O₃ to BaO is below 0.5; 10) The ratio of 10×Bi₂O₃ / BaO is 0.1–3.0; 11) The ratio of Bi₂O₃ to Sb₂O₃ is 0.1–10.0; 12)(CaO+TiO2) / B2O3 is below 0.

8. The Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3, and RO is the total content of BaO, SrO, CaO, and MgO.

6. The glass article having a blackened layer according to any one of claims 1 to 4, characterized in that, Its components are expressed as a weight percentage and satisfy one or more of the following 12 conditions: 1) The SiO2 / BaO ratio is 4.0–7.0; 2) (SiO2+K2O) / (B2O3+Al2O3) is 2.5~8.0; 3) The ratio of Na₂O / (Na₂O+K₂O) is 0.15–0.35; 4) The BaO / Na2O ratio is 3.0–15.0; 5) BaO / ZnO is 1.2~8.0; 6) ZnO / (Na2O+K2O) is 0.2~3.0; 7) (ZnO+BaO) / (SiO2+Na2O) is 0.15~0.45; 8) ZnO / (RO+Ln2O3) is 0.1~0.8; 9) The ratio of Ln₂O₃ to BaO is below 0.3; 10) The ratio of 10×Bi₂O₃ / BaO is 0.2–2.0; 11) The Bi₂O₃ / Sb₂O₃ ratio is 0.5–8.0; 12)(CaO+TiO2) / B2O3 is below 0.

6. The Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3, and RO is the total content of BaO, SrO, CaO, and MgO.

7. The glass article having a blackened layer according to any one of claims 1 to 4, characterized in that, Its components are expressed as a weight percentage and meet one or more of the following 11 conditions: 1) The SiO2 / BaO ratio is 4.2–5.5; 2) The ratio of (SiO2+K2O) / (B2O3+Al2O3) is 3.0 to 7.

0. 3) The BaO / Na2O ratio is 4.0–10.0; 4) BaO / ZnO is 1.5~5.0; 5) ZnO / (Na2O+K2O) is 0.4~2.0; 6) (ZnO+BaO) / (SiO2+Na2O) is 0.2~0.4; 7) ZnO / (RO+Ln2O3) is 0.2~0.7; 8) The ratio of Ln₂O₃ to BaO is below 0.2; 9) The ratio of 10×Bi₂O₃ / BaO is 0.25–1.0; 10) The Bi₂O₃ / Sb₂O₃ ratio is 1.0–6.0; 11)(CaO+TiO2) / B2O3 is below 0.

5. The Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3, and RO is the total content of BaO, SrO, CaO, and MgO.

8. The glass article having a blackened layer according to any one of claims 1 to 4, characterized in that, Its components are expressed as a weight percentage and meet one or more of the following nine conditions: 1) (SiO2+K2O) / (B2O3+Al2O3) is 3.5~5.0; 2) The BaO / Na2O ratio is 5.0–7.5; 3) BaO / ZnO is 1.8~3.0; 4) ZnO / (Na2O+K2O) is 0.5~1.0; 5) (ZnO+BaO) / (SiO2+Na2O) is 0.23~0.37; 6) ZnO / (RO+Ln2O3) is 0.25~0.6; 7) The ratio of Ln₂O₃ to BaO is below 0.1; 8) The Bi₂O₃ / Sb₂O₃ ratio is 1.0–4.0; 9) The ratio of (CaO+TiO2) / B2O3 is below 0.

2. The Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3, and RO is the total content of BaO, SrO, CaO, and MgO.

9. The glass article having a blackened layer according to any one of claims 1 to 4, characterized in that, Its components are expressed as weight percentages, wherein: SiO2: 52-65%; and / or B2O3: 8-18%; and / or BaO: 8-17%; and / or ZnO: 2-8%; and / or K2O: 1-8%; and / or Na2O: 0.5-4.8%; and / or Sb2O3: 0.05-1.5%; and / or Bi2O3: 0.05-3%; and / or Al2O3: 1-6%; and / or SrO: 0-3%; and / or MgO: 0-3%; and / or CaO: 0-3%; and / or Ln2O3: 0-3%; and / or ZrO2: 0-3%; and / or TiO2: 0-1%; and / or P2O5: 0-1%; and / or SnO2: 0-0.5%, wherein Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

10. The glass article having a blackening layer according to any one of claims 1 to 4, characterized in that, Its components are expressed as weight percentages, wherein: SiO2: 56-61%; and / or B2O3: 10-15%; and / or BaO: 10-15%; and / or ZnO: 3-7%; and / or K2O: 3-7%; and / or Na2O: 1-4.8%; and / or Sb2O3: 0.1-1%; and / or Bi2O3: 0.1-1%; and / or Al2O3: 2-5%; and / or SrO: 0-1%; and / or MgO: 0-1%; and / or CaO: 0-1%; and / or Ln2O3: 0-2%; and / or ZrO2: 0-2%; and / or TiO2: 0-0.5%; and / or P2O5: 0-0.5%; and / or SnO2: 0-0.2%, wherein Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

11. The glass article having a blackened layer according to any one of claims 1 to 4, characterized in that, Its components are expressed as a weight percentage, and it also contains: As2O3: 0-2%.

12. The glass article having a blackened layer according to any one of claims 1 to 4, characterized in that, Its components are expressed as a weight percentage, and it also contains: As2O3: 0-1%.

13. The glass article having a blackened layer according to any one of claims 1 to 4, characterized in that, Its components are expressed as a weight percentage, and it also contains: As2O3: 0-0.5%.

14. The glass article having a blackening layer according to any one of claims 1 to 4, characterized in that, Its components do not contain As2O3.

15. The glass article having a blackened layer according to any one of claims 1 to 4, characterized in that, Its components do not contain MgO; and / or do not contain SrO; and / or do not contain CaO; and / or do not contain TiO2; and / or do not contain ZrO2; and / or do not contain P2O5; and / or do not contain Ln2O3; and / or do not contain SnO2; and / or do not contain PbO, wherein Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

16. The glass article having a blackened layer according to any one of claims 1 to 2, characterized in that, The coefficient of thermal expansion α of the glass product with a blackened layer 0-300℃ 45×10 -7 / K~75×10 -7 / K.

17. The glass article having a blackening layer according to any one of claims 1 to 4, characterized in that, The density ρ of the glass product with the blackened layer is 3.00 g / cm³. 3 The following; and / or the coefficient of thermal expansion α 0-300℃ 50×10 -7 / K~70×10 -7 / K; and / or acid resistance stability D A Class 2 or above; and / or water resistance stability D W Class 2 or above; and / or weather resistance CR is Class 2 or above; and / or transition temperature T g The upper limit of the crystallization temperature is 570–610℃; and / or the upper limit of the crystallization temperature T. max Below 1050℃.

18. The glass article having a blackened layer according to any one of claims 1 to 4, characterized in that, The density ρ of the glass article with the blackened layer is 2.90 g / cm³. 3 The following; and / or the coefficient of thermal expansion α 0-300℃ 55×10 -7 / K~65×10 -7 / K; and / or acid resistance stability D A Class 1; and / or water resistance stability D W Class 1; and / or weather resistance CR is Class 1; and / or transition temperature T g The upper limit of the crystallization temperature is 575–605℃; and / or the upper limit of the crystallization temperature T. max Below 1000℃.

19. The glass article having a blackened layer according to any one of claims 1 to 4, characterized in that, The density ρ of the glass product with the blackened layer is 2.80 g / cm³. 3 The following; and / or the coefficient of thermal expansion α 0-300℃ 57×10 -7 / K~62×10 -7 / K; and / or transition temperature T g The upper limit of the crystallization temperature is 580–600℃; and / or the upper limit of the crystallization temperature T. max Below 950℃.

20. The glass article having a blackened layer according to any one of claims 1 to 4, characterized in that, The density ρ of the glass article with the blackened layer is 2.70 g / cm³. 3 The following; and / or transition temperature T g The upper limit of the crystallization temperature is 580–595℃; and / or the upper limit of the crystallization temperature T. max It is below 900℃.

21. The glass article having a blackened layer according to any one of claims 1 to 2, characterized in that, For glass products with a blackened layer thickness of less than 10 mm, the light transmittance of the blackened layer portion in the 400-900 nm range is ≤3.0%; for glass products with a blackened layer thickness of less than 10 mm, the light transmittance of the transparent portion in the 400-900 nm range is ≥90.0%.

22. The glass article having a blackened layer according to any one of claims 1 to 4, characterized in that, For glass products with a blackened layer thickness of less than 10 mm, the light transmittance of the blackened layer portion in the 400-900 nm range is ≤2.0%; for glass products with a blackened layer thickness of less than 10 mm, the light transmittance of the transparent portion in the 400-900 nm range is ≥90.5%.

23. The glass article having a blackening layer according to any one of claims 1 to 4, characterized in that, For glass products with a blackened layer thickness of less than 10 mm, the light transmittance of the blackened layer portion in the 400-900 nm range is ≤1.0%; for glass products with a blackened layer thickness of less than 10 mm, the light transmittance of the transparent portion in the 400-900 nm range is ≥91.0%.

24. The glass article having a blackening layer according to any one of claims 1 to 4, characterized in that, For glass products with a blackened layer thickness of less than 10 mm, the light transmittance of the blackened layer portion in the 400-900 nm range is ≤0.5%; for glass products with a blackened layer thickness of less than 10 mm, the light transmittance of the transparent portion in the 400-900 nm range is ≥91.5%.

25. The glass article with a blackened layer according to claim 22, characterized in that, The thickness is 1 to 8 mm.

26. The glass article with a blackening layer according to claim 22, characterized in that, The thickness is 2 to 6 mm.

27. The glass article with a blackening layer according to claim 22, characterized in that, The thickness is 3-5 mm.

28. A matrix glass, characterized in that, Its composition, expressed as a weight percentage, contains: SiO2: 51–68%; B2O3: 6–19%; BaO: 6–19%; ZnO: 1–10%; K2O: 0.5–10%; Na2O: greater than 0 but less than or equal to 4.8%; Sb2O3: greater than 0 but less than or equal to 2%, of which SiO2 / BaO is 3.0–11.0, 10×Bi2O3 / BaO is 0.05–4.0, Na2O / (Na2O+K2O) is 0.05–0.5, and it does not contain Li2O.

29. The matrix glass according to claim 28, characterized in that, Its components, expressed as a weight percentage, also contain: Bi2O3: 0.05–4%; and / or Al2O3: 0–8%; and / or SrO: 0–5%; and / or MgO: 0–5%; and / or CaO: 0–5%; and / or Ln2O3: 0–5%; and / or ZrO2: 0–5%; and / or TiO2: 0–2%; and / or P2O5: 0–3%; and / or SnO2: 0–1%, wherein the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

30. The matrix glass according to claim 28 or 29, characterized in that, Its components are expressed as a weight percentage and satisfy one or more of the following 12 conditions: 1) The SiO2 / BaO ratio is 3.5–10.0; 2)(SiO2+K2O) / (B2O3+Al2O3) is 2.0~10.0; 3) The ratio of Na₂O / (Na₂O+K₂O) is 0.1–0.5; 4) The BaO / Na2O ratio is 2.0–20.0; 5) BaO / ZnO is 1.0~10.0; 6) ZnO / (Na2O+K2O) is 0.1~5.0; 7) (ZnO+BaO) / (SiO2+Na2O) is 0.1~0.5; 8) ZnO / (RO+Ln2O3) is 0.05~1.0; 9) The ratio of Ln₂O₃ to BaO is below 0.5; 10) The ratio of 10×Bi₂O₃ / BaO is 0.1–3.0; 11) The ratio of Bi₂O₃ to Sb₂O₃ is 0.1–10.0; 12)(CaO+TiO2) / B2O3 is below 0.

8. The Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3, and RO is the total content of BaO, SrO, CaO, and MgO.

31. The matrix glass according to claim 28 or 29, characterized in that, Its components are expressed as a weight percentage and satisfy one or more of the following 12 conditions: 1) The SiO2 / BaO ratio is 4.0–7.0; 2) (SiO2+K2O) / (B2O3+Al2O3) is 2.5~8.0; 3) The ratio of Na₂O / (Na₂O+K₂O) is 0.15–0.35; 4) The BaO / Na2O ratio is 3.0–15.0; 5) BaO / ZnO is 1.2~8.0; 6) ZnO / (Na2O+K2O) is 0.2~3.0; 7) (ZnO+BaO) / (SiO2+Na2O) is 0.15~0.45; 8) ZnO / (RO+Ln2O3) is 0.1~0.8; 9) The ratio of Ln₂O₃ to BaO is below 0.3; 10) The ratio of 10×Bi₂O₃ / BaO is 0.2–2.0; 11) The Bi₂O₃ / Sb₂O₃ ratio is 0.5–8.0; 12)(CaO+TiO2) / B2O3 is below 0.

6. The Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3, and RO is the total content of BaO, SrO, CaO, and MgO.

32. The matrix glass according to claim 28 or 29, characterized in that, Its components are expressed as a weight percentage and meet one or more of the following 11 conditions: 1) The SiO2 / BaO ratio is 4.2–5.5; 2) The ratio of (SiO2+K2O) / (B2O3+Al2O3) is 3.0 to 7.

0. 3) The BaO / Na2O ratio is 4.0–10.0; 4) BaO / ZnO is 1.5~5.0; 5) ZnO / (Na2O+K2O) is 0.4~2.0; 6) (ZnO+BaO) / (SiO2+Na2O) is 0.2~0.4; 7) ZnO / (RO+Ln2O3) is 0.2~0.7; 8) The ratio of Ln₂O₃ to BaO is below 0.2; 9) The ratio of 10×Bi₂O₃ / BaO is 0.25–1.0; 10) The Bi₂O₃ / Sb₂O₃ ratio is 1.0–6.0; 11)(CaO+TiO2) / B2O3 is below 0.

5. The Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3, and RO is the total content of BaO, SrO, CaO, and MgO.

33. The matrix glass according to claim 28 or 29, characterized in that, Its components are expressed as a weight percentage and meet one or more of the following nine conditions: 1) (SiO2+K2O) / (B2O3+Al2O3) is 3.5~5.0; 2) The BaO / Na2O ratio is 5.0–7.5; 3) BaO / ZnO is 1.8~3.0; 4) ZnO / (Na2O+K2O) is 0.5~1.0; 5) (ZnO+BaO) / (SiO2+Na2O) is 0.23~0.37; 6) ZnO / (RO+Ln2O3) is 0.25~0.6; 7) The ratio of Ln₂O₃ to BaO is below 0.1; 8) The Bi₂O₃ / Sb₂O₃ ratio is 1.0–4.0; 9) The ratio of (CaO+TiO2) / B2O3 is below 0.

2. The Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3, and RO is the total content of BaO, SrO, CaO, and MgO.

34. The matrix glass according to claim 28 or 29, characterized in that, Its components are expressed as weight percentages, wherein: SiO2: 52-65%; and / or B2O3: 8-18%; and / or BaO: 8-17%; and / or ZnO: 2-8%; and / or K2O: 1-8%; and / or Na2O: 0.5-4.8%; and / or Sb2O3: 0.05-1.5%; and / or Bi2O3: 0.05-3%; and / or Al2O3: 1-6%; and / or SrO: 0-3%; and / or MgO: 0-3%; and / or CaO: 0-3%; and / or Ln2O3: 0-3%; and / or ZrO2: 0-3%; and / or TiO2: 0-1%; and / or P2O5: 0-1%; and / or SnO2: 0-0.5%, wherein Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

35. The matrix glass according to claim 28 or 29, characterized in that, Its components are expressed as weight percentages, including: SiO2: 56–61%; and / or B2O3: 10–15%; and / or BaO: 8–17%, preferably BaO: 10–15%; and / or ZnO: 3–7%; and / or K2O: 3–7%; and / or Na2O: 1–4.8%; and / or Sb2O3: 0.1–1%; and / or Bi2O3: 0.1–1%; and / or Al2O3 : 2-5%; and / or SrO: 0-1%; and / or MgO: 0-1%; and / or CaO: 0-1%; and / or Ln2O3: 0-2%; and / or ZrO2: 0-2%; and / or TiO2: 0-0.5%; and / or P2O5: 0-0.5%; and / or SnO2: 0-0.2%, wherein Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

36. The matrix glass according to claim 28 or 29, characterized in that, Its components are expressed as a weight percentage, and it also contains: As2O3: 0-2%.

37. The matrix glass according to claim 28 or 29, characterized in that, Its components are expressed as a weight percentage, and it also contains: As2O3: 0-1%.

38. The matrix glass according to claim 28 or 29, characterized in that, Its components are expressed as a weight percentage, and it also contains: As2O3: 0-0.5%.

39. The matrix glass according to claim 28 or 29, characterized in that, Its components do not contain As2O3.

40. The matrix glass according to claim 28 or 29, characterized in that, Its components do not contain MgO; and / or do not contain SrO; and / or do not contain CaO; and / or do not contain TiO2; and / or do not contain ZrO2; and / or do not contain P2O5; and / or do not contain Ln2O3; and / or do not contain SnO2; and / or do not contain PbO, wherein Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

41. The matrix glass according to claim 28 or 29, characterized in that, The refractive index n of the matrix glass d The value is 1.50–1.56; and / or the Abbe number v. d It is 60-66; and / or the density ρ is 3.00 g / cm³. 3 The following; and / or the coefficient of thermal expansion α 0-300℃ 45×10 -7 / K~75×10 -7 / K; and / or acid resistance stability D A Class 2 or above; and / or water resistance stability D W Class 2 or above; and / or weather resistance CR is Class 2 or above; and / or transition temperature T g The upper limit of the crystallization temperature is 570–610℃; and / or the upper limit of the crystallization temperature T. max Below 1050℃.

42. The matrix glass according to claim 28 or 29, characterized in that, The refractive index n of the matrix glass d The value is 1.51 to 1.55; and / or the Abbe number v. d The value is 61–65; and / or the density ρ is 2.90 g / cm³. 3 The following; and / or the coefficient of thermal expansion α 0-300℃ 50×10 -7 / K~70×10 -7 / K; and / or acid resistance stability D A Class 1; and / or water resistance stability D W Class 1; and / or weather resistance CR is Class 1; and / or transition temperature T g The upper limit of the crystallization temperature is 575–605℃; and / or the upper limit of the crystallization temperature T. max Below 1000℃.

43. The matrix glass according to claim 28 or 29, characterized in that, The refractive index n of the matrix glass d The range is 1.515 to 1.54; and / or the Abbe number v. d It is 62-64; and / or the density ρ is 2.80 g / cm³. 3 The following; and / or the coefficient of thermal expansion α 0-300℃ 55×10 -7 / K~65×10 -7 / K; and / or transition temperature T g The upper limit of the crystallization temperature is 580–600℃; and / or the upper limit of the crystallization temperature T. max Below 950℃.

44. The matrix glass according to claim 28 or 29, characterized in that, The density ρ of the matrix glass is 2.70 g / cm³. 3 The following; and / or the coefficient of thermal expansion α 0-300℃ 57×10 -7 / K~62×10 -7 / K; and / or transition temperature T g The upper limit of the crystallization temperature is 580–595℃; and / or the upper limit of the crystallization temperature T. max It is below 900℃.

45. The matrix glass according to claim 28 or 29, characterized in that, The light transmittance τ of the matrix glass before blackening treatment 前400-900nm ≥90.0%; and / or light transmittance τ after blackening treatment. 后400-900nm ≤3.0%.

46. ​​The matrix glass according to claim 28 or 29, characterized in that, The light transmittance τ of the matrix glass before blackening treatment 前400-900nm ≥90.5%; and / or light transmittance τ after blackening treatment 后400-900nm ≤2.0%.

47. The matrix glass according to claim 28 or 29, characterized in that, The light transmittance τ of the matrix glass before blackening treatment 前400-900nm ≥91.0%; and / or light transmittance τ after blackening treatment 后400-900nm ≤1.0%.

48. The matrix glass according to claim 28 or 29, characterized in that, The light transmittance τ of the matrix glass before blackening treatment 前400-900nm ≥91.5%; and / or light transmittance τ after blackening treatment 后400-900nm ≤0.5%.

49. An optical element, characterized in that, It is made of glass articles having a blackened layer as described in any one of claims 1 to 27, or of matrix glass as described in any one of claims 28 to 48.

50. An optical instrument, characterized in that, A glass article containing a blackened layer as described in any one of claims 1 to 27, and / or a matrix glass as described in any one of claims 28 to 48, and / or an optical element as described in claim 49.

51. The method for manufacturing a glass article having a blackened layer according to any one of claims 1 to 27, characterized in that, The method includes the following steps: 1) forming a matrix glass; 2) processing the glass mold; 3) blackening treatment; 4) shaping treatment.

52. The method for manufacturing a glass article with a blackened layer according to claim 51, characterized in that, The glass molding process includes using direct drip molding, and / or grinding, and / or polishing, and / or molding to form a glass molded body with a certain shape from the substrate glass, the glass molded body having a 2D, 2.5D or 3D structure.

53. The method for manufacturing a glass article with a blackened layer according to claim 51, characterized in that, The blackening treatment involves placing the glass molded body in a reducing atmosphere at a certain temperature for a certain period of time; the temperature is T. g Temperatures below -10℃; blackening treatment time is 50 to 1000 hours.

54. The method for manufacturing a glass article with a blackened layer according to claim 51, characterized in that, The blackening treatment involves placing the glass molded body in a reducing atmosphere at a specific temperature for a certain period of time. The reducing atmosphere is either hydrogen or carbon monoxide; the temperature is T. g -10℃~T g -200℃; blackening treatment time is 100 to 800 hours.

55. The method for manufacturing a glass article with a blackened layer according to claim 51, characterized in that, The blackening treatment involves placing the glass molded body in a reducing atmosphere at a specific temperature for a certain period of time. The reducing atmosphere is either hydrogen or carbon monoxide; the temperature is T. g -20℃~T g -100℃; blackening treatment time is 200-700 hours.

56. The method for manufacturing a glass article with a blackened layer according to claim 51, characterized in that, The blackening treatment involves placing the glass molded body in a reducing atmosphere at a specific temperature (hydrogen gas) for a certain period of time; the temperature is T. g -20℃~T g -60℃; blackening treatment time is 300-600 hours.

57. The method for manufacturing a glass article with a blackened layer according to claim 51, characterized in that, The blackening treatment involves placing the glass molded body in a reducing atmosphere at a specific temperature (hydrogen gas) for a certain period of time; the temperature is T. g -30℃~T g -50℃; blackening treatment time is 300-600 hours.

58. The method for manufacturing a glass article with a blackened layer according to claim 51, characterized in that, The shaping process involves processing a specific area of ​​the blackened glass body to remove the blackened layer from that area, making that specific area of ​​the glass transparent while other areas retain the blackened layer.

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