阅读说明：本技术 环保玻璃材料 (Environment-friendly glass material ) 是由 毛露路 郝良振 李赛 匡波 张鹏 于 2020-06-30 设计创作，主要内容包括：本发明提供一种环保玻璃材料,其组分中含有SiO<Sub>2</Sub>、ZnO、碱金属氧化物和S,但不含有Cd；所述环保玻璃材料的厚度为3mm时,截止波长为550nm以上,800～850nm的透过率为75％以上,850～900nm的透过率为80％以上,900～1000nm的透过率为83％以上,1000～2000nm的透过率为85％以上。通过合理的组分设计,本发明的玻璃材料在实现环保化的同时,实现紫外和可见光截止,以及近红外高的透过率。(The invention provides an environment-friendly glass material, which contains SiO in the components 2 ZnO, alkali metal oxide and S, but no Cd; when the thickness of the environment-friendly glass material is 3mm, the cut-off wavelength is more than 550nm, the transmittance of 800-850 nm is more than 75%, the transmittance of 850-900 nm is more than 80%, the transmittance of 900-1000 nm is more than 83%, and the transmittance of 1000-2000 nm is more than 85%. Through reasonable component design, the glass material realizes ultraviolet and visible light cutoff and high near-infrared transmittance while realizing environmental protection.)

1. The environment-friendly glass material is characterized in that the components contain SiO₂ZnO, alkali metal oxide and S, but no Cd; when the thickness of the environment-friendly glass material is 3mm, the cutoff wavelength is more than 550nm, the transmittance of 800-850 nm is more than 75%, and the transmittance of 850-900 nm isThe transmittance is 80% or more, the transmittance is 83% or more at 900 to 1000nm, and the transmittance is 85% or more at 1000 to 2000 nm.

2. The eco-glass material according to claim 1, wherein the eco-glass material has a cutoff wavelength of 600nm or more, preferably 650nm or more, more preferably 680nm or more, and still more preferably 700nm or more, when the thickness is 3 mm.

3. The eco-glass material according to claim 1, wherein the transmittance at 800 to 850nm is 77% or more, preferably 80% or more, when the thickness of the eco-glass material is 3 mm.

4. The eco-glass material according to claim 1, wherein the eco-glass material has a transmittance of 850 to 900nm of 82% or more, preferably a transmittance of 850 to 900nm of 83% or more, when the thickness of the eco-glass material is 3 mm.

5. The eco-glass material according to claim 1, wherein the eco-glass material has a transmittance of 900 to 1000nm of 84% or more, preferably a transmittance of 900 to 1000nm of 85% or more, when the thickness of the eco-glass material is 3 mm.

6. The eco-glass material according to claim 1, wherein the eco-glass material has a transmittance of 86% or more at 1000 to 2000nm, preferably 87% or more at 1000 to 2000nm, when the thickness of the eco-glass material is 3 mm.

7. The environmentally friendly glass material of claim 1, wherein the composition comprises, in weight percent: SiO 2₂：35～80％；ZnO：5～35％；Na₂O：5～25％；K₂O：1～10％；S：0.2～8％；Sb+Ag+Ce+Sn+Te+V+Fe：0.5～10％。

8. The environmentally friendly glass material of claim 7, further comprising, in weight percent: li₂O: 0 to 5 percent; and/or B₂O₃: 0 to 10 percent; and/or Al₂O₃: 0 to 5 percent; and/or MgO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or SrO: 0 to 10 percent; and/or BaO: 0 to 10 percent; and/or; se: 0 to 5 percent; and/or F: 0 to 5 percent.

9. The environment-friendly glass material is characterized by comprising the following components in percentage by weight: SiO 2₂：35～80％；ZnO：5～35％；Na₂O：5～25％；K₂O：1～10％；Li₂O：0～5％；S：0.2～8％；Sb+Ag+Ce+Sn+Te+V+Fe：0.5～10％；B₂O₃：0～10％；Al₂O₃: 0 to 5 percent; MgO: 0 to 5 percent; CaO: 0 to 5 percent; SrO: 0 to 10 percent; BaO: 0 to 10 percent; se: 0 to 5 percent; f: 0-5% and no Cd.

10. The environmentally friendly glass material according to any one of claims 1 to 9, wherein the composition comprises, in weight percent: SiO 2₂: 40-75%; and/or ZnO: 7-30%; and/or Na₂O: 7-22%; and/or K₂O: 2-8%; and/or Li₂O: 0 to 3 percent; and/or S: 0.5-7%; and/or Sb + Ag + Ce + Sn + Te + V + Fe: 0.8-9%; and/or B₂O₃: 0 to 5 percent; and/or Al₂O₃: 0 to 3 percent; and/or MgO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or Se: 0 to 4 percent; and/or F: 0 to 3 percent.

11. The environmentally friendly glass material according to any one of claims 1 to 9, wherein the composition comprises, in weight percent: SiO 2₂: 42-73%; and/or ZnO: 9-25%; and/or Na₂O: 8-19%; and/or K₂O: 3-7%; and/or S: 1-6%; and/or Sb + Ag + Ce + Sn + Te + V + Fe:0.9-8%; and/or Se: 0 to 3 percent; and/or Li₂O: 0-2%; and/or B₂O₃: 0 to 3 percent; and/or Al₂O₃: 0 to 1 percent; and/or MgO: 0-2%; and/or CaO: 0-2%; and/or SrO: 0-2%; and/or BaO: 0-2%; and/or F: 0 to 1 percent.

12. The environmentally friendly glass material according to any one of claims 1 to 9, wherein the composition comprises, in weight percent: CuO + TiO₂+P₂O₅: 0 to 0.5%, preferably CuO + TiO₂+P₂O₅: 0.0001-0.5%, more preferably CuO + TiO₂+P₂O₅: 0.0001-0.4%, preferably CuO + TiO₂+P₂O₅：0.0001～0.3％。

13. The environmentally friendly glass material according to any one of claims 1 to 9, wherein the composition is expressed in weight percentage, wherein: b is₂O₃/SiO₂Is 0.23 or less, preferably B₂O₃/SiO₂Is 0.15 or less, more preferably B₂O₃/SiO₂Is 0.1 or less.

14. The environmentally friendly glass material according to any one of claims 1 to 9, wherein the composition is expressed in weight percentage, wherein: ZnO/SiO₂0.07 to 0.95, preferably ZnO/SiO₂0.10 to 0.75, and more preferably ZnO/SiO₂0.15 to 0.60.

15. The environmentally friendly glass material according to any one of claims 1 to 9, wherein the composition is expressed in weight percentage, wherein: Se/S is 1.5 or less, preferably 1.3 or less, more preferably 1.0 or less, and further preferably 0.5 or less.

16. The environmentally friendly glass material according to any one of claims 1 to 9, wherein the composition is expressed in weight percentage, wherein: (Sb + Ag + Ce + Sn + Te + V + Fe)/(Se + S) is 0.1 to 25.0, preferably (Sb + Ag + Ce + Sn + Te + V + Fe)/(S + Se) is 0.2 to 15.0, more preferably (Sb + Ag + Ce + Sn + Te + V + Fe)/(S + Se) is 0.5 to 8.0, and still more preferably (Sb + Ag + Ce + Sn + Te + V + Fe)/(S + Se) is 1.0 to 5.0.

17. The environmentally friendly glass material according to any one of claims 1 to 9, wherein the composition is expressed in weight percentage, wherein: (Ag + Ce + Sn + Te + V + Fe)/Sb is 3.0 or less, preferably (Ag + Ce + Sn + Te + V + Fe)/Sb is 2.0 or less, more preferably (Ag + Ce + Sn + Te + V + Fe)/Sb is 1.0 or less, and still more preferably (Ag + Ce + Sn + Te + V + Fe)/Sb is 0.8 or less.

18. The environmentally friendly glass material according to any one of claims 1 to 9, wherein the composition is expressed in weight percentage, wherein: li₂O+Na₂O+K₂O is 8 to 35%, and Li is preferable₂O+Na₂O+K₂O is 9 to 30%, and Li is more preferable₂O+Na₂O+K₂O is 10 to 22%.

19. The eco-friendly glass material according to any one of claims 1 to 9, wherein B is not contained₂O₃(ii) a And/or do not contain Li₂O; and/or no Sn; and/or no Te.

20. The eco-glass material according to claim 9, wherein the eco-glass material has a cutoff wavelength of 550nm or more, preferably a cutoff wavelength of 600nm or more, more preferably a cutoff wavelength of 650nm or more, further preferably 680nm or more, and further preferably 700nm or more, when the thickness is 3 mm.

21. The eco-friendly glass material according to claim 9, wherein the eco-friendly glass material has a transmittance of 800 to 850nm of 75% or more, preferably a transmittance of 800 to 850nm of 77% or more, and more preferably a transmittance of 800 to 850nm of 80% or more, when the thickness of the eco-friendly glass material is 3 mm; and/or when the thickness of the environment-friendly glass material is 3mm, the transmittance of 850-900 nm is more than 80%, preferably the transmittance of 850-900 nm is more than 82%, and more preferably the transmittance of 850-900 nm is more than 83%; and/or when the thickness of the environment-friendly glass material is 3mm, the transmittance of 900-1000 nm is more than 83%, preferably the transmittance of 900-1000 nm is more than 84%, and more preferably the transmittance of 900-1000 nm is more than 85%; and/or when the thickness of the environment-friendly glass material is 3mm, the transmittance of 1000-2000 nm is more than 85%, preferably the transmittance of 1000-2000 nm is more than 86%, and more preferably the transmittance of 1000-2000 nm is more than 87%.

22. The eco-glass material according to any one of claims 1 to 9, wherein the eco-glass material has an acid resistance stability of 3 or more, preferably 2 or more, more preferably 1 or more, and/or a water resistance stability of 3 or more, preferably 2 or more, more preferably 1 or more, and/or a thermal expansion coefficient of 80 × 10^-7More than/K, preferably 85 × 10^-7More preferably 90 × 10K or more, and still more preferably 90 ×^-7More preferably 95 × 10K or more, and still more preferably 95 ×^-7More than K.

23. The glass preform is characterized by being made of the environment-friendly glass material according to any one of claims 1 to 22.

24. A glass member, characterized by being made of the eco-friendly glass material according to any one of claims 1 to 22 or the glass preform according to claim 23.

25. An apparatus comprising the eco-friendly glass material according to any one of claims 1 to 22, and/or comprising the glass element according to claim 24.

26. The method for producing an environmentally friendly glass material as claimed in any one of claims 1 to 22, wherein the method comprises the steps of:

1) mixing the raw materials according to the component proportion of the environment-friendly glass material, and putting the uniformly mixed raw materials into a 1300-1500 ℃ smelting furnace for smelting to form molten glass;

2) stirring and homogenizing the molten glass;

3) pouring or leaking molten glass into a mold for molding;

4) further processing the glass formed in the step 3) or the glass formed in the step 3) into a glass prefabricated member or a glass element, and then preserving the glass at 470-600 ℃ for 10-60 hours for color development treatment.

27. The method for producing an eco-glass material according to claim 26, wherein a compound salt, and/or a hydroxide, and/or an oxide, and/or a sulfide, and/or a selenide, and/or a fluoride, and/or a simple substance is used as a raw material of the eco-glass material.

Technical Field

The invention relates to a glass material, in particular to an environment-friendly glass material with ultraviolet and visible light cut-off and high near-infrared transmittance.

Background

In recent years, with the development of the photoelectric industry, the detection application degree of the near-infrared band of 800nm to 2000nm is higher, especially for intelligent equipment, near-infrared laser is urgently needed to realize real-time perception of the surrounding environment, so that decision is provided for the action and movement of the intelligent equipment, and the realization is based on the fact that an optical system is needed to filter out ultraviolet and visible light bands which interfere with the near-infrared working band, and high transmittance is required in the near-infrared band.

The traditional selenium-cadmium glass can cut off ultraviolet visible wave bands, and has high near infrared wave band transmittance, but has the defects that the glass contains a large amount of cadmium (Cd), cannot meet the existing environmental protection standard, and brings huge harm to the environment and human bodies in various links such as production, use, abandonment and the like; in addition, the selenium-cadmium glass has poor chemical stability and is not suitable for intelligent equipment which needs to bear severe environment.

Disclosure of Invention

The invention aims to provide an environment-friendly glass material with ultraviolet and visible light cut-off and high near-infrared transmittance.

The technical scheme adopted by the invention for solving the technical problem is as follows:

(1) the environment-friendly glass material comprises the components of SiO₂ZnO, alkali metal oxide and S, but no Cd; when the thickness of the environment-friendly glass material is 3mm, the cut-off wavelength is more than 550nm, the transmittance of 800-850 nm is more than 75%, the transmittance of 850-900 nm is more than 80%, the transmittance of 900-1000 nm is more than 83%, and the transmittance of 1000-2000 nm is more than 85%.

(2) The eco-friendly glass material according to (1), wherein the eco-friendly glass material has a cutoff wavelength of 600nm or more, preferably 650nm or more, more preferably 680nm or more, and still more preferably 700nm or more, when the thickness of the eco-friendly glass material is 3 mm.

(3) The environment-friendly glass material according to the item (1), wherein when the thickness of the environment-friendly glass material is 3mm, the transmittance at 800-850 nm is 77% or more, and preferably the transmittance at 800-850 nm is 80% or more.

(4) The environmentally-friendly glass material according to the item (1), wherein when the thickness of the environmentally-friendly glass material is 3mm, the transmittance at 850-900 nm is 82% or more, preferably the transmittance at 850-900 nm is 83% or more.

(5) The environment-friendly glass material in the (1), wherein when the thickness of the environment-friendly glass material is 3mm, the transmittance of 900-1000 nm is more than 84%, and preferably the transmittance of 900-1000 nm is more than 85%.

(6) The environment-friendly glass material according to the item (1), wherein when the thickness of the environment-friendly glass material is 3mm, the transmittance at 1000 to 2000nm is 86% or more, and preferably the transmittance at 1000 to 2000nm is 87% or more.

(7) The environment-friendly glass material in the step (1) comprises the following components in percentage by weight: SiO 2₂：35～80％；ZnO：5～35％；Na₂O：5～25％；K₂O：1～10％；S：0.2～8％；Sb+Ag+Ce+Sn+Te+V+Fe：0.5～10％。

(8) The environment-friendly glass material according to the item (7), which comprises the following components in percentage by weight: li₂O: 0 to 5 percent; and/or B₂O₃: 0 to 10 percent; and/or Al₂O₃: 0 to 5 percent; and/or MgO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or SrO: 0 to 10 percent; and/or BaO: 0 to 10 percent; and/or; se: 0 to 5 percent; and/or F: 0 to 5 percent.

(9) The environment-friendly glass material comprises the following components in percentage by weight: SiO 2₂：35～80％；ZnO：5～35％；Na₂O：5～25％；K₂O：1～10％；Li₂O：0～5％；S：0.2～8％；Sb+Ag+Ce+Sn+Te+V+Fe：0.5～10％；B₂O₃：0～10％；Al₂O₃: 0 to 5 percent; MgO: 0 to 5 percent; CaO: 0 to 5 percent; SrO: 0 to 10 percent; BaO: 0 to 10 percent; se: 0 to 5 percent; f: 0-5% and no Cd.

(10) The environment-friendly glass material according to any one of (1) to (9), which comprises the following components in percentage by weight: SiO 2₂: 40-75%; and/or ZnO: 7-30%; and/or Na₂O: 7-22%; and/or K₂O：2～8％；And/or Li₂O: 0 to 3 percent; and/or S: 0.5-7%; and/or Sb + Ag + Ce + Sn + Te + V + Fe: 0.8-9%; and/or B₂O₃: 0 to 5 percent; and/or Al₂O₃: 0 to 3 percent; and/or MgO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or Se: 0 to 4 percent; and/or F: 0 to 3 percent.

(11) The environment-friendly glass material according to any one of (1) to (9), which comprises the following components in percentage by weight: SiO 2₂: 42-73%; and/or ZnO: 9-25%; and/or Na₂O: 8-19%; and/or K₂O: 3-7%; and/or S: 1-6%; and/or Sb + Ag + Ce + Sn + Te + V + Fe: 0.9-8%; and/or Se: 0 to 3 percent; and/or Li₂O: 0-2%; and/or B₂O₃: 0 to 3 percent; and/or Al₂O₃: 0 to 1 percent; and/or MgO: 0-2%; and/or CaO: 0-2%; and/or SrO: 0-2%; and/or BaO: 0-2%; and/or F: 0 to 1 percent.

(12) The environment-friendly glass material according to any one of (1) to (9), which comprises the following components in percentage by weight: CuO + TiO₂+P₂O₅: 0 to 0.5%, preferably CuO + TiO₂+P₂O₅: 0.0001-0.5%, more preferably CuO + TiO₂+P₂O₅: 0.0001-0.4%, preferably CuO + TiO₂+P₂O₅：0.0001～0.3％。

(13) The environment-friendly glass material according to any one of (1) to (9), which comprises the following components in percentage by weight: b is₂O₃/SiO₂Is 0.23 or less, preferably B₂O₃/SiO₂Is 0.15 or less, more preferably B₂O₃/SiO₂Is 0.1 or less.

(14) The environment-friendly glass material according to any one of (1) to (9), which comprises the following components in percentage by weight: ZnO/SiO₂0.07 to 0.95, preferably ZnO/SiO₂0.10 to 0.75, and more preferably ZnO/SiO₂0.15 to 0.60.

(15) The environment-friendly glass material according to any one of (1) to (9), which comprises the following components in percentage by weight: Se/S is 1.5 or less, preferably 1.3 or less, more preferably 1.0 or less, and further preferably 0.5 or less.

(16) The environment-friendly glass material according to any one of (1) to (9), which comprises the following components in percentage by weight: (Sb + Ag + Ce + Sn + Te + V + Fe)/(Se + S) is 0.1 to 25.0, preferably (Sb + Ag + Ce + Sn + Te + V + Fe)/(S + Se) is 0.2 to 15.0, more preferably (Sb + Ag + Ce + Sn + Te + V + Fe)/(S + Se) is 0.5 to 8.0, and still more preferably (Sb + Ag + Ce + Sn + Te + V + Fe)/(S + Se) is 1.0 to 5.0.

(17) The environment-friendly glass material according to any one of (1) to (9), which comprises the following components in percentage by weight: (Ag + Ce + Sn + Te + V + Fe)/Sb is 3.0 or less, preferably (Ag + Ce + Sn + Te + V + Fe)/Sb is 2.0 or less, more preferably (Ag + Ce + Sn + Te + V + Fe)/Sb is 1.0 or less, and still more preferably (Ag + Ce + Sn + Te + V + Fe)/Sb is 0.8 or less.

(18) The environment-friendly glass material according to any one of (1) to (9), which comprises the following components in percentage by weight: li₂O+Na₂O+K₂O is 8 to 35%, and Li is preferable₂O+Na₂O+K₂O is 9 to 30%, and Li is more preferable₂O+Na₂O+K₂O is 10 to 22%.

(19) The eco-friendly glass material according to any one of (1) to (9), which does not contain B₂O₃(ii) a And/or do not contain Li₂O; and/or no Sn; and/or no Te.

(20) The eco-friendly glass material according to (9), wherein the eco-friendly glass material has a cutoff wavelength of 550nm or more, preferably 600nm or more, more preferably 650nm or more, further preferably 680nm or more, and further preferably 700nm or more, when the thickness of the eco-friendly glass material is 3 mm.

(21) The environmentally-friendly glass material according to the item (9), wherein when the thickness of the environmentally-friendly glass material is 3mm, the transmittance at 800 to 850nm is 75% or more, preferably the transmittance at 800 to 850nm is 77% or more, and more preferably the transmittance at 800 to 850nm is 80% or more; and/or when the thickness of the environment-friendly glass material is 3mm, the transmittance of 850-900 nm is more than 80%, preferably the transmittance of 850-900 nm is more than 82%, and more preferably the transmittance of 850-900 nm is more than 83%; and/or when the thickness of the environment-friendly glass material is 3mm, the transmittance of 900-1000 nm is more than 83%, preferably the transmittance of 900-1000 nm is more than 84%, and more preferably the transmittance of 900-1000 nm is more than 85%; and/or when the thickness of the environment-friendly glass material is 3mm, the transmittance of 1000-2000 nm is more than 85%, preferably the transmittance of 1000-2000 nm is more than 86%, and more preferably the transmittance of 1000-2000 nm is more than 87%.

(22) The eco-friendly glass material according to any one of (1) to (9), wherein the eco-friendly glass material has an acid resistance stability of 3 or more, preferably 2 or more, and more preferably 1 or more, and/or a water resistance stability of 3 or more, preferably 2 or more, and more preferably 1 or more, and/or a thermal expansion coefficient of 80 × 10^-7More than/K, preferably 85 × 10^-7More preferably 90 × 10K or more, and still more preferably 90 ×^-7More preferably 95 × 10K or more, and still more preferably 95 ×^-7More than K.

(23) The glass preform is made of the environment-friendly glass material in any one of (1) to (22).

(24) A glass member made of the eco-friendly glass material according to any one of (1) to (22) or the glass preform according to (23).

(25) An apparatus comprising the eco-glass material according to any one of (1) to (22), and/or comprising the glass element according to (24).

(26) The method for producing an eco-friendly glass material according to any one of (1) to (22), the method comprising the steps of:

1) mixing the raw materials according to the component proportion of the environment-friendly glass material, and putting the uniformly mixed raw materials into a 1300-1500 ℃ smelting furnace for smelting to form molten glass;

2) stirring and homogenizing the molten glass;

3) pouring or leaking molten glass into a mold for molding;

4) further processing the glass formed in the step 3) or the glass formed in the step 3) into a glass prefabricated member or a glass element, and then preserving the glass at 470-600 ℃ for 10-60 hours for color development treatment.

(27) The method for producing an eco-friendly glass material according to (26), wherein a compound salt, and/or a hydroxide, and/or an oxide, and/or a sulfide, and/or a selenide, and/or a fluoride, and/or a simple substance is used as a raw material of the eco-friendly glass material.

The invention has the beneficial effects that: through reasonable component design, the glass material realizes ultraviolet and visible light cutoff and high near-infrared transmittance while realizing environmental protection.

Drawings

FIG. 1 is a graph showing the spectral transmittance of the eco-glass material of example 2 of the present invention.

Detailed Description

The embodiments of the present invention will be described in detail below, but the present invention is not limited to the embodiments described below, and can be implemented with appropriate modifications within the scope of the object of the present invention. Although the description of the overlapping portions may be omitted as appropriate, the invention is not limited thereto, and the eco-glass material of the present invention may be simply referred to as glass in the following description.

[ Environment-friendly glass Material ]

The ranges of the components (ingredients) of the eco-friendly glass material of the present invention are explained below. In the present specification, the contents and total contents of the respective components are all expressed by weight percent (wt%), unless otherwise specified.

Unless otherwise indicated herein, the numerical ranges set forth herein include upper and lower values, and the terms "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.

< essential Components and optional Components >

SiO₂Is one of the main components of the glass, in which a suitable amount of SiO is present₂Can stabilize coloring so that the glass can achieve the desired cut-off properties, while a suitable amount of SiO₂Can improve the chemical stability of the glassAnd (5) performing qualitative determination. If SiO₂The content of (A) is less than 35%, the cut-off performance of the glass cannot meet the design requirement, and the chemical stability of the glass is rapidly reduced. Thus, in the present invention, SiO₂The lower limit of (B) is 35%, preferably 40%, more preferably 42%. If SiO₂The content of the glass is higher than 80%, the melting temperature of the glass is sharply increased, the volatilization of coloring substances is increased, and the cut-off performance of the glass is reduced; meanwhile, the high-temperature viscosity of the glass is increased rapidly, and bubbles and inclusions in the product are increased greatly. Thus, SiO in the present invention₂The upper limit of the content of (B) is 80%, preferably 75%, more preferably 73%.

B₂O₃The melting performance of the glass can be improved in the glass, and the inherent quality and chemical stability of the glass are improved. However, the present inventors have found, through their studies, that B₂O₃In the glass, a change in the glass structure is caused, and the threshold for the binding of coloring matter substances is increased, so that the cut-off capability of the glass is lowered. Therefore, when the glass cut-off ability satisfies the requirement, B may be contained in an amount of 10% or less₂O₃For improving the melting behavior and chemical stability of the glass, preferably B₂O₃The content of (b) is 5% or less, more preferably 3% or less. In some embodiments, it is further preferred not to contain B₂O₃。

The present invention has been discovered, through a number of experimental studies, in some embodiments by combining B with B₂O₃/SiO₂Below 0.23, the water-resistant action stability of the glass can be improved while the glass cut-off performance is optimized. Preferably B₂O₃/SiO₂Is 0.15 or less, more preferably B₂O₃/SiO₂Is 0.1 or less.

ZnO in the glass can improve the chemical stability of the glass, reduce the high-temperature viscosity of the glass and can be in SiO₂The volatilization of the coloring matter is reduced in the smelting stage, and meanwhile, the structural transformation of the coloring matter can be promoted, and the cut-off performance of the glass is improved. If the content of ZnO is less than 5 percent, the cut-off performance of the glass can not meet the requirement, and the chemical stability of the glass is reduced. Therefore, the lower limit of the ZnO content is 5%, preferablyThe lower limit is 7%, and the lower limit is more preferably 9%. If the content of ZnO exceeds 35%, the glass is easy to crystallize, and the near infrared transmittance of the glass is greatly reduced particularly in the forming and annealing stages. Therefore, the upper limit of the content of ZnO is 35%, preferably 30%, more preferably 25%.

In some embodiments of the invention, if ZnO/SiO₂The value of (A) is less than 0.07, the chemical stability of the glass does not meet the design requirement, and the cut-off capability of the glass is reduced. If ZnO/SiO₂The value of (A) is higher than 0.95, the glass is easy to crystallize by non-coloring substances, and the near infrared transmittance, especially the transmittance of 800-1000 nm, is easy to rapidly decrease. Therefore, ZnO/SiO is preferred₂When the value of (A) is between 0.07 and 0.95, more preferably between 0.10 and 0.75, and still more preferably between 0.15 and 0.60, the threshold value for the formation of the glass coloring matter is reduced, which is favorable for the improvement of the cut-off performance and the near-infrared transmittance.

Li₂O、Na₂O、K₂O is an alkali metal oxide, and in the glass of the present invention, the high temperature viscosity of the glass can be reduced, and bubbles and inclusions in the glass can be reduced. The high-temperature viscosity is reduced, the solubility of coloring substances can be improved, and the cut-off performance of the glass is improved. In addition, the alkali metal oxide can provide more free oxygen, and the near infrared transmittance of the glass can be improved while the better cut-off performance is realized. However, if the content is less than 8%, the above effect is not significant, and the expansion coefficient of the glass is lower than the design target, and the glass cannot be well matched with a material with a high expansion coefficient and high hardness for use. If the content is more than 35%, the glass becomes liable to devitrify, resulting in a decrease in the cut-off property and near infrared transmittance of the glass and a rapid decrease in the chemical stability. Therefore, the total content Li of the alkali metal oxides₂O+Na₂O+K₂O is 8 to 35%, preferably 9 to 30%, more preferably 10 to 22%.

Li₂O has very strong capability of reducing the high-temperature viscosity of the glass, and is beneficial to improving the inherent quality of the glass in the glass. However, the present inventors have found that Li ions have a strong ability to aggregate in glass and interfere with the structural transition of coloring matterIn other words, the cut-off properties of the glass are thereby reduced, and especially in the case where the content thereof is more than 5%, the glass does not achieve the desired cut-off properties. Therefore, Li is preferable₂The content of O is 5% or less, more preferably 3% or less, and still more preferably 2% or less. In some embodiments, it is even more preferred not to contain Li₂O。

Na₂O in the glass can reduce the high-temperature viscosity of the glass, reduce the structural change threshold of coloring substances, simultaneously improve the near infrared transmittance of the glass, improve the thermal expansion coefficient of the glass and facilitate the coupling of the glass and a high-strength transparent material. If Na₂The content of O is lower than 5%, the near infrared transmittance of the glass cannot meet the design requirement, the cut-off performance of the glass is reduced, and the thermal expansion coefficient of the glass is lower than the design requirement. Thus, Na₂The lower limit of the content of O is 5%, preferably 7%, more preferably 8%. If Na₂The content of O is more than 25%, the chemical stability of the glass is lowered, the glass is easily crystallized, the threshold value of structural change of the coloring matter substance is increased, and the glass cutoff performance is lowered. Thus, Na₂The upper limit of the content of O is 25%, preferably 22%, more preferably 19%.

In the present glass system, K₂Action of O with Na₂O is similar to but in comparison with Na₂O has strong capability of improving near infrared; on the other hand, K₂The ratio of the capacity of O to reduce the chemical stability of the glass to the capacity of the glass to resist devitrification is Na₂O is stronger. Therefore, K is determined from the viewpoint of optimizing the chemical stability, devitrification resistance and cut-off ability of the glass₂The content of O is limited to 1 to 10%, preferably 2 to 8%, more preferably 3 to 7%.

Al₂O₃The chemical stability of the glass can be improved in the glass, but the cut-off performance of the glass can also be reduced, if the content of the Al exceeds 5 percent, the cut-off performance of the glass can not meet the design requirement, so the Al₂O₃The content of (b) is 5% or less, preferably 3% or less. If the glass has a chemical stability margin, Al is more preferable₂O₃The content of (B) is 1% or less.

MgO can improve the chemical stability of the glass, but if the content thereof exceeds 5%, the devitrification resistance of the glass is lowered, resulting in a reduction in the cut-off capability of the glass and a reduction in the near infrared transmittance of the glass. Therefore, the content of MgO is limited to 5% or less, preferably 3% or less, and more preferably 2% or less.

CaO can improve the stability and anti-crystallization performance of the glass and reduce the high-temperature viscosity of the glass. If the content exceeds 5%, the formation of a structure of a coloring matter substance is disturbed, and the cut-off property of the glass is lowered. Therefore, the content of CaO is limited to 5% or less, preferably 3% or less, and more preferably 2% or less.

Suitable amounts of BaO and SrO in the glass improve the chemical stability of the glass, increase the hardness of the glass and increase the near infrared transmittance of the glass, but if the content thereof exceeds 10%, the ability of the glass to fix coloring matter is reduced, with the risk of lowering the cut-off ability. Therefore, the contents of BaO and SrO are each limited to 10% or less, preferably 5% or less, and more preferably 2% or less.

F can improve the melting performance of the glass in the glass, reduce the volatilization of coloring substances in the feeding stage and improve the cut-off performance of the glass. However, if the content exceeds 5%, the high-temperature viscosity of the glass rapidly decreases, and excessive volatilization of coloring matter substances is caused. Therefore, the content of F is 5% or less, preferably 3% or less, more preferably 1% or less, and it is more preferable not to contain F from the viewpoint of environmental protection.

S can form coloring substances with Sb, Ag, Ce, Sn, Te, V, Fe and the like in the glass, so that the glass generates cut-off absorption in a wave band of 500-720 nm. If the S content exceeds 8%, the glass is liable to devitrify and the near-infrared transmittance is drastically reduced; if the content is less than 0.2%, the cut-off property of the glass does not meet the design requirement. Therefore, the S content is limited to 0.2 to 8%, preferably 0.5 to 7%, and more preferably 1 to 6%. The S content in the invention refers to the content of all sulfur in all sulfur-containing substances in the glass converted into elemental sulfur. S can be introduced in the present invention by means of elemental sulfur and/or sulfur-containing compounds.

Se can form coloring matters with Sb, Ag, Ce, Sn, Te, V, Fe and the like in the glass, so that the glass generates cut-off absorption in a wave band of 650-1200 nm, and the cut-off performance is superior to that of an S simple substance or sulfide. When the content of Se exceeds 5%, the glass is likely to be crystallized and the near-infrared transmittance is rapidly decreased. Therefore, the content of Se in the glass of the present system is 5% or less, preferably 4% or less, more preferably 3% or less, and when the cut-off performance meets the design requirement, it is more preferable that Se is not contained. The Se content refers to the content of selenium in all selenium-containing substances in the glass which is converted into elemental selenium. In the present invention, Se may be introduced by means of elemental selenium and/or selenium-containing compounds.

Through a large amount of experimental researches, the invention discovers that in some embodiments, if the value of Se/S is more than 1.5, the transmittance of 800-1000 nm of the glass can not meet the design requirement. Therefore, the value of Se/S is preferably 1.5 or less, more preferably 1.3 or less, still more preferably 1.0 or less, and still more preferably 0.5 or less.

One or more of Sb, Ag, Ce, Sn, Te, V and Fe may form a coloring compound with S and/or Se in the glass of the present invention, and if the total content of Sb + Ag + Ce + Sn + Te + V + Fe exceeds 10%, the glass becomes liable to devitrify, resulting in a sharp decrease in near-infrared transmittance. If the total content of Sb + Ag + Ce + Sn + Te + V + Fe is less than 0.5%, the amount of coloring matter formed in the glass is small and the designed cut-off performance cannot be achieved. Therefore, the content of Sb + Ag + Ce + Sn + Te + V + Fe is 0.5-10%, preferably 0.8-9%, and more preferably 0.9-8%. The Sb + Ag + Ce + Sn + Te + V + Fe content in the invention refers to the total content of Sb in all Sb-containing substances, Ag in Ag-containing substances, Ce in Ce-containing substances, Sn in Sn-containing substances, Te in Te-containing substances, V in V-containing substances and Fe in Fe-containing substances in glass after all the Sb, Ag, Ce, Sn, Te, V and Fe in the Sb-containing substances are converted into simple substances. Sb, Ag, Ce, Sn, Te, V, and Fe may be introduced by way of oxides, and/or sulfides, and/or selenides, and/or fluorides, and/or simple substances, and/or complex salts, and/or hydroxides, and the like. In some embodiments of the present invention, it is preferred that Sn and/or Te are not included.

In some embodiments of the invention, if (Sb + Ag + Ce + Sn + Te + V + Fe)/(S + Se) is less than 0.1, the near infrared transmittance of the glass decreases significantly; if the (Sb + Ag + Ce + Sn + Te + V + Fe)/(S + Se) exceeds 25.0, the cut-off performance of the glass is obviously reduced, and the anti-devitrification capability of the glass is sharply reduced. Therefore, it is preferable that the value of (Sb + Ag + Ce + Sn + Te + V + Fe)/(S + Se) is 0.1 to 25.0, more preferable that the value of (Sb + Ag + Ce + Sn + Te + V + Fe)/(S + Se) is 0.2 to 15.0, still more preferable that the value of (Sb + Ag + Ce + Sn + Te + V + Fe)/(S + Se) is 0.5 to 8.0, and still more preferable that the value of (Sb + Ag + Ce + Sn + Te + V + Fe)/(S + Se) is 1.0 to 5.0.

In some embodiments of the invention, there is a synergistic effect when Sb, Ag, Ce, Sn, Te, V, Fe form a coloring matter with anions in the glass, and the near infrared transmittance of the glass is greatly reduced when the value of (Ag + Ce + Sn + Te + V + Fe)/Sb is greater than 3.0. Therefore, the value of (Ag + Ce + Sn + Te + V + Fe)/Sb is preferably 3.0 or less, more preferably 2.0 or less, still more preferably 1.0 or less, and still more preferably 0.8 or less.

In some embodiments of the present invention, CuO and TiO may be additionally contained₂、P₂O₅One or more of which promote the formation of colouring substances in the glass according to the invention, but CuO, TiO₂、P₂O₅Total content of CuO + TiO₂+P₂O₅Above 0.5%, the glass is particularly liable to devitrify, and the structure of the coloring matter substance is adversely changed to drastically lower the near infrared transmittance, so that CuO + TiO₂+P₂O₅The content of (B) is 0.5% or less. On the other hand, if CuO + TiO₂+P₂O₅Below 0.0001%, coloring matter can only be formed depending on the impurity defects in the glass, resulting in problems of poor cut-off performance, poor coloring uniformity of the glass, and the like. Therefore, CuO + TiO is preferred₂+P₂O₅0.0001 to 0.5%, preferably 0.0001 to 0.4%, and more preferably 0.0001 to 0.3%. The CuO and TiO of the invention₂、P₂O₅In the amount of (A), which is not included in the CuO and TiO components except for the one described in the present invention₂、P₂O₅The content of all other components except the above components is 100 wt%.

< component which should not be contained >

To be environmentally friendly, the glass of the invention does not contain Cd, As and Pb.

"0%" or "free" as used herein means that the compound, molecule or element is not intentionally added as a raw material to the glass of the present invention, but that the compound, molecule or element is not intentionally added as a raw material and/or equipment for producing the glass, and that the compound, molecule or element is not intentionally added, and is contained in a small amount or a trace amount in the final glass.

Next, the properties of the eco-friendly glass material of the present invention will be described.

< cut-off Performance >

A3 mm glass sample is tested for the transmittance curve of 300nm to 2000nm of the glass by using a spectrometer according to the GB/T7962.12-2010 method, and the transmittance becomes a cut-off wavelength at 5%. For the purposes of the present invention, a higher cutoff value indicates better cutoff performance of the glass, and a lower cutoff value indicates poorer cutoff performance.

In some embodiments of the present invention, the eco-glass material has a cutoff wavelength of 550nm or more, preferably a cutoff wavelength of 600nm or more, more preferably a cutoff wavelength of 650nm or more, still more preferably 680nm or more, and still more preferably 700nm or more.

< near Infrared transmittance >

A3 mm glass sample is tested by a spectrometer according to a GB/T7962.12-2010 method to obtain a transmittance curve of 300 nm-2000 nm of glass, and the near-infrared transmittance of the invention refers to a transmittance value of 800 nm-2000 nm. The near infrared transmittance refers to the lowest transmittance in the corresponding waveband range.

In some embodiments of the invention, the eco-friendly glass material of the invention has one or more of the following:

1) a transmittance of 800 to 850nm of 75% or more, preferably a transmittance of 800 to 850nm of 77% or more, more preferably a transmittance of 800 to 850nm of 80% or more;

2) a transmittance of 850 to 900nm of 80% or more, preferably a transmittance of 850 to 900nm of 82% or more, more preferably a transmittance of 850 to 900nm of 83% or more;

3) a transmittance of 83% or more at 900 to 1000nm, preferably 84% or more at 900 to 1000nm, and more preferably 85% or more at 900 to 1000 nm;

4) a transmittance of 85% or more at 1000 to 2000nm, preferably 86% or more at 1000 to 2000nm, and more preferably 87% or more at 1000 to 2000 nm.

< stability against acid Effect >

Stability of the acid resistance of the glass (D)_A) (powder method) the test was carried out according to the method prescribed in GB/T17129. Acid resistance stability is sometimes referred to herein simply as acid resistance or acid resistance stability.

In some embodiments of the invention, the environmentally friendly glass material has stability against acid action (D)_A) Is 3 or more, preferably 2 or more, and more preferably 1.

< stability against Water action >

Stability of the glass to Water action (D)_W) (powder method) the test was carried out according to the method prescribed in GB/T17129. Stability to hydrolytic action is sometimes referred to herein simply as water resistance or hydrolytic stability.

In some embodiments of the invention, the water action resistant stability of the eco-glass material (D)_W) Is 3 or more, preferably 2 or more, and more preferably 1.

< coefficient of thermal expansion >

The thermal expansion coefficient of the invention is the average thermal expansion coefficient of the glass at 20-300 ℃, which is α_20-300℃The test is shown to be carried out according to the method specified in GB/T7962.16-2010.

In some embodiments of the invention, the eco-glass material has an average coefficient of thermal expansion (α)_20-300℃) Is 80 × 10^-7More than/K, preferably 85 × 10^-7More preferably 90 × 10K or more, and still more preferably 90 ×^-7More preferably 95 × 10K or more, and still more preferably 95 ×^-7More than K.

[ production method ]

The manufacturing method of the environment-friendly glass material comprises the following steps:

1) mixing the raw materials according to the component proportion of the environment-friendly glass material, and putting the uniformly mixed raw materials into a 1300-1500 ℃ smelting furnace for smelting to form molten glass;

2) stirring and homogenizing the molten glass;

3) pouring or leaking molten glass into a mold for molding;

4) preserving the glass formed in the step 3) at 470-600 ℃ for 10-60 hours for color development treatment; or further processing the glass formed in the step 3) into a glass prefabricated member or a glass element, and then preserving the glass at 470-600 ℃ for 10-60 hours for color development treatment.

Further, the raw material of the above-mentioned environmentally friendly glass material may use a compound salt (such as carbonate, sulfate, nitrate, etc.), and/or a hydroxide, and/or an oxide, and/or a sulfide, and/or a selenide, and/or a fluoride, and/or a simple substance, etc.

[ glass preform and glass Member ]

The glass preform can be produced from the produced eco-friendly glass material by means of, for example, grinding or press molding such as reheat press molding or precision press molding. That is, the glass preform may be produced by machining the green glass material by grinding, polishing, or the like, or by producing a preform for press molding from the green glass material, reheat-pressing the preform, and then polishing, or by precision press-molding the preform obtained by polishing.

It should be noted that the means for producing the glass preform is not limited to the above means.

The glass preform and the glass element of the present invention are both formed of the above-described eco-friendly glass material of the present invention. The glass prefabricated member has excellent characteristics of an environment-friendly glass material; the glass element of the present invention has excellent characteristics of an environmentally friendly glass material, and can provide glass elements such as various filters, lenses, prisms, and the like, which have high value.

[ apparatus ]

The environment-friendly glass material and the glass element formed by the environment-friendly glass material can be used for manufacturing devices such as optical filters, photographic devices, camera devices, display devices, monitoring devices, electronic devices, intelligent devices and the like.