CN113045199A - Ultraviolet-transmitting glass - Google Patents
Ultraviolet-transmitting glass Download PDFInfo
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- CN113045199A CN113045199A CN202110310627.7A CN202110310627A CN113045199A CN 113045199 A CN113045199 A CN 113045199A CN 202110310627 A CN202110310627 A CN 202110310627A CN 113045199 A CN113045199 A CN 113045199A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0085—Compositions for glass with special properties for UV-transmitting glass
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides ultraviolet-transmitting glass, which comprises the following components in percentage by weight: SiO 22：55～70％；B2O3：2～18％；ZnO：1～20％；La2O3+Y2O3+Gd2O3：4～30％；Ta2O5+Nb2O5+TiO2+ZrO2：0.5～20％；Li2O+Na2O+K2O: 3 to 15% of (La)2O3+Y2O3+Gd2O3)/B2O30.3 to 6.0. Through reasonable component design, the glass obtained by the invention has higher ultraviolet transmittance and excellent chemical stability.
Description
Technical Field
The invention relates to ultraviolet-transmitting glass, in particular to ultraviolet-transmitting glass with excellent chemical stability.
Background
In recent years, 320-400 nm band ultraviolet light is widely applied in the fields of anti-counterfeiting currency detection, food packaging, metal detection, blood analysis, ultraviolet packaging, ultraviolet lithography, ultraviolet exposure systems and the like. With the rapid development of the semiconductor manufacturing field, the requirements of ultraviolet packaging, ultraviolet lithography and ultraviolet exposure systems on precision are higher and higher. Taking the objective system of the ultraviolet lithography machine as an example, several or even ten large-aperture lenses with different refractive indexes and abbe numbers are required to be combined to realize the effect of high precision. Therefore, the demand for glass having high ultraviolet transmittance in the field of photoelectric information is rapidly increasing.
Glass is subject to attack by various liquids in the environment (such as acids, alkalis, water, etc.) during production and use, and therefore the resistance of glass to such attack, i.e., the chemical stability of the glass, is critical to the accuracy and longevity of the instrument. CN106977096A discloses glass with high ultraviolet band transmittance, but the glass contains 60-70% of phosphoric acid and 13-15% of boric acid by mass percent, and the chemical stability of the glass is poor.
Disclosure of Invention
The invention aims to provide ultraviolet-transmitting glass with excellent chemical stability.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(1) the ultraviolet-transmitting glass comprises the following components in percentage by weight: SiO 22：55～70％；B2O3：2～18％；ZnO：1～20％；La2O3+Y2O3+Gd2O3：4～30％；Ta2O5+Nb2O5+TiO2+ZrO2：0.5～20％；Li2O+Na2O+K2O: 3 to 15% of (La)2O3+Y2O3+Gd2O3)/B2O30.3 to 6.0.
(2) The ultraviolet-transmitting glass according to (1), which comprises the following components in percentage by weight: BaO + SrO + CaO + MgO: 0 to 15 percent; and/or Al2O3: 0 to 5 percent; and/or F: 0 to 3 percent; and/or a clarifying agent: 0-1% of a clarifying agent Sb2O3、SnO、SnO2、CeO2One or more of Cl and Br.
(3) UV-transparent glass containing SiO2、B2O3ZnO and alkali metal oxide as essential components in weight percentageThe La content is 4-30% by weight2O3+Y2O3+Gd2O3Wherein (La)2O3+Y2O3+Gd2O3)/B2O30.3 to 6.0, the refractive index n of the ultraviolet transmitting glassd1.51 to 1.58, Abbe number vdIs 55 to 65, tau365nmIs more than 99.0%.
(4) The ultraviolet-transmitting glass according to the item (3), which comprises the following components in percentage by weight: SiO 22: 55-70%; and/or B2O3: 2-18%; and/or ZnO: 1-20%; and/or Ta2O5+Nb2O5+TiO2+ZrO2: 0.5-20%; and/or Li2O+Na2O+K2O: 3-15%; and/or BaO + SrO + CaO + MgO: 0 to 15 percent; and/or Al2O3: 0 to 5 percent; and/or F: 0 to 3 percent; and/or a clarifying agent: 0-1% of a clarifying agent Sb2O3、SnO、SnO2、CeO2One or more of Cl and Br.
(5) The ultraviolet-transmitting glass according to any one of (1) to (4), which has a composition satisfying, in terms of weight percent, one or more of the following 6 conditions:
1)(La2O3+Y2O3+Gd2O3)/(Ta2O5+Nb2O5+TiO2+ZrO2) 1.0 to 13.0, preferably (La)2O3+Y2O3+Gd2O3)/(Ta2O5+Nb2O5+TiO2+ZrO2) 2.0 to 10.0, more preferably (La)2O3+Y2O3+Gd2O3)/(Ta2O5+Nb2O5+TiO2+ZrO2) 3.0 to 7.0;
2)La2O3/Nb2O5is 3.5 to 15.0, preferably La2O3/Nb2O55.0 to 14.0, more preferably La2O3/Nb2O57.0 to 13.5;
3)(La2O3+Y2O3+Gd2O3)/SiO20.07 to 0.35, preferably (La)2O3+Y2O3+Gd2O3)/SiO20.08 to 0.3, more preferably (La)2O3+Y2O3+Gd2O3)/SiO20.1 to 0.25;
4)(B2O3+Al2O3)/SiO20.05 to 0.4, preferably (B)2O3+Al2O3)/SiO20.08 to 0.35, more preferably (B)2O3+Al2O3)/SiO20.1 to 0.3;
5)(BaO+SrO+CaO+MgO)/SiO20.01 to 0.25, preferably (BaO + SrO + CaO + MgO)/SiO20.02 to 0.2, more preferably (BaO + SrO + CaO + MgO)/SiO20.02 to 0.1;
6)(La2O3+Y2O3+Gd2O3)/B2O30.4 to 5.0, preferably (La)2O3+Y2O3+Gd2O3)/B2O30.5 to 3.0.
(6) The ultraviolet-transmitting glass according to any one of (1) to (4), which comprises, in terms of weight percent: SiO 22: 56-68%, preferably SiO2: 57-67%; and/or B2O3: 4 to 16%, preferably B2O3: 5-15%; and/or ZnO: 2-16%, preferably ZnO: 3-12%; and/or La2O3+Y2O3+Gd2O3: 5 to 20%, preferably La2O3+Y2O3+Gd2O3: 7-15%; and/or Ta2O5+Nb2O5+TiO2+ZrO2: 1 to 15%, preferably Ta2O5+Nb2O5+TiO2+ZrO2: 2-10%; and/or Li2O+Na2O+K2O: 5 to 14%, preferably Li2O+Na2O+K2O: 6-13%; and/or BaO + SrO + CaO + MgO: 1-15%, preferably BaO + SrO + CaO + MgO: 1.5-10%, more preferably BaO + SrO + CaO + MgO: 1.5-8%; and/or Al2O3: 0 to 4%, preferably Al2O3: 0 to 3 percent; and/or F: 0-2%, preferably F: 0 to 1 percent; and/or a clarifying agent: 0-0.8%, preferably clarifying agent: 0-0.5%, the clarifying agent is Sb2O3、SnO、SnO2、CeO2One or more of Cl and Br.
(7) The ultraviolet-transmitting glass according to any one of (1) to (4), which comprises, in terms of weight percent: la2O3: 4-25%, preferably La2O3: 6 to 20%, more preferably La2O3: 7-14%; and/or Gd2O3: 0 to 8%, preferably Gd2O3: 0 to 7%, more preferably Gd2O3: 0 to 5 percent; and/or Y2O3: 0 to 10%, preferably Y2O3: 0 to 8%, more preferably Y2O3: 0 to 5 percent; and/or Na2O: 2-15%, preferably Na2O: 4 to 14%, more preferably Na2O: 5-13%; and/or K2O: 0 to 8%, preferably K2O: 1 to 6%, more preferably K2O: 2-5%; and/or Li2O: 0 to 5%, preferably Li2O: 0 to 4%, more preferably Li2O：0～3％。
(8) The ultraviolet-transmitting glass according to any one of (1) to (4) having a refractive index nd1.51 to 1.58, preferably 1.52 to 1.57, more preferably 1.53 to 1.56, and/or an Abbe number vdIs 55 to 65, preferably 56 to 63, and more preferably 57 to 60.
(9) τ of the ultraviolet-transmitting glass according to any one of (1) to (4)365nm99.0% or more, preferably 99.2% or more, more preferably 99.4% or more, still more preferably 99.5% or more, and/or Δ τ365nmIs 5.0% or less, preferably 2.0% or less, and more preferably 1.0% or less.
(10) The ultraviolet-transmitting glass according to any one of (1) to (4) having stability to water action DWIs 2 or more, preferably 1; and/or stability against acid action DAIs 3 or more, preferably 2 or more, more preferably 1; and/or a temperature coefficient of refractive index dn/dt of 8.0 x 10-6Preferably 7.0X 10 or less/° C-6Lower than/° C, more preferably 6.0X 10-6Below/° c; and/or the upper limit temperature of crystallization is 1300 ℃ or lower, preferably 1280 ℃ or lower, more preferably 1250 ℃ or lower, and still more preferably 1230 ℃ or lower; and/or the degree of bubbling is class A or more, preferably class A0More preferably A or more00A stage; and/or the degree of streaking is at least level C, preferably at least level B; and/or Δ ndValue of 5X 10-6Hereinafter, 3 × 10 is preferable-6Hereinafter, more preferably 2 × 10-6The following.
(11) The glass preform is made of the ultraviolet-transmitting glass of any one of (1) to (10).
(12) An optical element produced from the ultraviolet-transmitting glass according to any one of (1) to (10), or the glass preform according to (11).
(13) An optical device comprising the ultraviolet-transmitting glass according to any one of (1) to (10), and/or comprising the optical element according to (12).
The invention has the beneficial effects that: through reasonable component design, the glass obtained by the invention has higher ultraviolet transmittance and excellent chemical stability.
Detailed Description
The present invention is not limited to the following embodiments, and can be carried out 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 gist of the present invention is not limited thereto, and the ultraviolet-transmitting glass of the present invention may be simply referred to as glass in the following description.
[ ultraviolet-transmitting glass ]
The ranges of the respective components (ingredients) of the ultraviolet-transmitting glass of the present invention are explained below. In the present invention, the contents and total contents of the respective components are all expressed in weight percent (wt%), that is, the contents and total contents of the respective components are expressed in weight percent with respect to the total amount of the glass substance converted into the composition of oxides, if not specifically stated. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the ultraviolet-transmitting glass composition component of the present invention are decomposed in the melt and converted to oxides, the total amount of the oxides is 100%.
Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. 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 >
SiO2And B2O3Is the main network former component of the glass of the invention, and the stable structure formed by the two network former components is the basis for realizing high transmittance of ultraviolet light and excellent chemical stability. If SiO2The content of the (B) is less than 55%, the transmittance of the glass at 365nm is low and cannot reach more than 99.0%, and the ultraviolet optical system with long light transmission path and high illumination requirement is fatal, such as a lens of a photoetching machine, a prism of an exposure machine and the like. Thus, SiO2The lower limit of (B) is 55%, preferably 56%, more preferably 57%. If SiO2The content of the iron (Fe) ions and the platinum (Pt) ions which have strong absorption effect on an ultraviolet band rapidly increase, and the ultraviolet transmittance, especially the transmittance at 365nm rapidly decreases. In addition, SiO2Too high content of (b) also results in too high temperature viscosity of the glass, and the optical uniformity, bubble degree and streak degree are difficult to meet the design requirements. Thus, it is possible to provide，SiO2The upper limit of the content of (B) is 70%, preferably 68%, more preferably 67%.
Appropriate amount of B2O3The refractive index of the glass can be improved, the structure of the glass is reinforced, and the ultraviolet radiation resistance of the glass is improved. If B is2O3The content of (b) is higher than 18%, the erosion of the glass liquid to the crucible is rapidly increased, and the ultraviolet transmittance is rapidly reduced. If B is2O3The content of (B) is less than 2%, and glass melting is difficult. Thus, B2O3The content of (b) is 2 to 18%, preferably 4 to 16%, more preferably 5 to 15%.
Al2O3The compactness of the internal structure of the glass can be improved, the ultraviolet transmittance and the chemical stability of the glass are improved, but if the content of the ultraviolet transmittance and the chemical stability exceeds 5 percent, stones are easily generated in the glass, and the internal quality of the glass is poor. Thus, Al2O3The content of (b) is limited to 5% or less, preferably 4% or less, and more preferably 3% or less.
SiO2、B2O3And Al2O3Can form a glass network, and the inventor finds out through a great deal of experimental research that when the three network forming components coexist, the structure of the glass is changed complexly, so that the properties of the glass, such as high-temperature viscosity, chemical stability and the like, are changed. In some embodiments, by controlling (B)2O3+Al2O3)/SiO2The value of (A) is in the range of 0.05 to 0.4, which can prevent the viscosity at high temperature from increasing while the glass has excellent chemical stability. Thus, (B)2O3+Al2O3)/SiO2The value of (b) is preferably 0.05 to 0.4, more preferably 0.08 to 0.35, and further preferably 0.1 to 0.3.
BaO, SrO, CaO and MgO are alkaline earth metal oxides, and the inventor finds that although the alkaline earth metal oxides can improve the refractive index and stability of the glass, the structure of the glass is not tight enough, so that the ultraviolet transmittance and the chemical stability of the glass are poor. When the total content of the alkaline earth metal oxides BaO + SrO + CaO + MgO in the glass of the present invention is more than 15%, the ultraviolet transmittance of the glass is greatly reduced, and therefore the total content of the alkaline earth metal oxides BaO + SrO + CaO + MgO in the glass of the present invention is 0 to 15%. On the other hand, if BaO + SrO + CaO + MgO is less than 1%, the effect of improving the stability of the glass is not obvious, and the tendency of devitrification of the glass is increased, which is very disadvantageous for the forming of large-sized glass (e.g., glass having a width of more than 330mm and a thickness of more than 30 mm). Therefore, the total content of the alkaline earth metal oxides BaO + SrO + CaO + MgO in the present invention is preferably 1 to 15%, more preferably 1.5 to 10%, and still more preferably 1.5 to 8%. In terms of selection of the kind of the alkaline earth metal oxide, BaO and/or SrO are preferable because they are most advantageous for improving the glass stability, BaO is more preferable, and CaO and/or MgO is further preferably not contained.
The inventors have found through extensive experimental studies that, in some embodiments, if (BaO + SrO + CaO + MgO)/SiO2When the value of (b) is more than 0.25, the refractive index of the glass can easily meet the design requirements, but the glass structure is damaged, the impurity level is increased, and the ultraviolet transmittance is rapidly reduced. Therefore, (BaO + SrO + CaO + MgO)/SiO in the present invention2The value of (d) is preferably 0.25 or less, more preferably 0.2 or less, and still more preferably 0.1 or less. On the other hand, by using (BaO + SrO + CaO + MgO)/SiO2The value of (A) is 0.01 or more, and the stability and chemical stability of the glass can be prevented from being lowered. Thus, (BaO + SrO + CaO + MgO)/SiO2The value of (b) is preferably 0.01 or more, more preferably 0.02 or more.
The ZnO with proper amount can strengthen the network structure of the glass and improve the refractive index and the ultraviolet transmittance of the glass. If the content of ZnO exceeds 20 percent, the phase separation tendency of the glass is increased, the ultraviolet transmittance is reduced on the contrary, and meanwhile, the degree of striae is difficult to meet the design requirement. On the other hand, if the content of ZnO is less than 1%, the effect of improving the ultraviolet transmittance of the glass is not obvious, the surface tension of the glass is increased, bubbles are not easy to remove, and the bubble degree is difficult to meet the design requirement. Therefore, the content of ZnO is 1 to 20%, preferably 2 to 16%, and more preferably 3 to 12%.
La2O3、Gd2O3、Y2O3Belongs to high-refractivity low-dispersion oxide, can quickly raise refractivity of glass in the glass and regulate dispersion of glass. The inventors found, through extensive studies, that La2O3、Gd2O3、Y2O3The glass has strong concentration, the stability of the glass structure can be improved, and the ultraviolet transmittance of the glass can be improved while the refractive index is improved; on the other hand, the proper amount of the glass can improve the ultraviolet radiation resistance of the glass, and can also reduce the viscosity of the glass, so that the glass is easier to melt, clarify and form, and is more favorable for obtaining high optical uniformity, bubble degree and streak degree. However, La2O3、Gd2O3、Y2O3If the content is too large, the glass becomes particularly liable to devitrify, and in the case of serious, the vitrification of the glass may even occur. Therefore, La is preferred in the present invention2O3、Gd2O3、Y2O3The total content La of2O3+Y2O3+Gd2O34 to 30%, preferably 5 to 20%, more preferably 7 to 15%.
Through continuous experimental research, the inventor finds that La improves the ultraviolet transmittance2O3Is superior to Y2O3，Y2O3Is superior to Gd2O3(ii) a In the aspect of improving the ultraviolet radiation resistance of glass, La2O3Slightly superior to Gd2O3，Gd2O3Is superior to Y2O3. Therefore, the La in the invention integrates the performances of ultraviolet transmittance, ultraviolet radiation resistance, crystallization resistance and the like of the glass2O3The content of (b) is preferably 4 to 25%, more preferably 6 to 20%, and further preferably 7 to 14%; y is2O3The content of (b) is preferably 0 to 10%, more preferably 0 to 8%, and further preferably 0 to 5%; gd (Gd)2O3The content of (b) is preferably 0 to 8%, more preferably 0 to 7%, and further preferably 0 to 5%.
The inventors have found, through extensive experimental studies, that, in some embodiments, (La) is2O3+Y2O3+Gd2O3)/SiO2A value of more than 0.35, stability and resistance to devitrification of the glassThe properties become poor and in severe cases ceramics are formed even during the flow of the glass stream. If (La)2O3+Y2O3+Gd2O3)/SiO2The value of (A) is less than 0.07, the viscosity of the glass at 1400 ℃ can exceed 400 poise, and under high viscosity, the bubble degree and the fringe degree in the production process can hardly meet the design requirements, and simultaneously, the ultraviolet transmittance of the glass can hardly meet the design requirements; more importantly, the structure of the glass tends to be relaxed, and the ultraviolet radiation resistance of the glass is reduced. Therefore, (La) is preferable2O3+Y2O3+Gd2O3)/SiO2The value of (A) is 0.07 to 0.35, more preferably (La)2O3+Y2O3+Gd2O3)/SiO2The value of (A) is 0.08 to 0.3, and (La) is more preferable2O3+Y2O3+Gd2O3)/SiO2The value of (b) is 0.1 to 0.25.
In some embodiments of the invention, if (La)2O3+Y2O3+Gd2O3)/B2O3The value of (A) exceeds 6.0, the devitrification resistance of the glass becomes poor; if (La)2O3+Y2O3+Gd2O3)/B2O3If the value of (A) is less than 0.3, the chemical stability of the glass is deteriorated and the ultraviolet transmittance is lowered. Therefore, (La) is preferable2O3+Y2O3+Gd2O3)/B2O3The value of (b) is 0.3 to 6.0, more preferably 0.4 to 5.0, and still more preferably 0.5 to 3.0.
Ta2O5、Nb2O5、TiO2、ZrO2The glass belongs to high-refraction and high-dispersion oxide, and the ultraviolet radiation resistance of the glass can be improved in the glass, and meanwhile, the refractive index and the dispersion of the glass can also be improved. In the invention making Ta2O5、Nb2O5、TiO2、ZrO2Total content Ta of2O5+Nb2O5+TiO2+ZrO2In the range of 0.5% or more to obtain the above effects, Ta is preferred2O5+Nb2O5+TiO2+ZrO2Is 1% or more, more preferably 2% or more. On the other hand, Ta2O5、Nb2O5、TiO2、ZrO2Has the function of reducing ultraviolet transmittance in glass, if Ta2O5、Nb2O5、TiO2、ZrO2Total content Ta of2O5+Nb2O5+TiO2+ZrO2Above 20%, the ultraviolet transmittance of the glass, particularly the transmittance at 365nm, hardly meets the design requirements. Thus, Ta2O5+Nb2O5+TiO2+ZrO2Is 20% or less, preferably 15% or less, more preferably 10% or less.
In the glass production process, if the upper limit crystallization temperature of the glass exceeds 1300 ℃, the molten glass is easy to block in each connection link of the smelting furnace, so that the transmittance, the internal quality, the streak degree and the like of the glass cannot meet the design requirements. The inventors have discovered, through extensive experimental studies, that in some embodiments, La can be controlled by controlling it2O3、Y2O3、Gd2O3The total content La of2O3+Y2O3+Gd2O3And Ta2O5、Nb2O5、TiO2、ZrO2Total content Ta of2O5+Nb2O5+TiO2+ZrO2Ratio of (La) to (C)2O3+Y2O3+Gd2O3)/(Ta2O5+Nb2O5+TiO2+ZrO2) When the glass is between 1.0 and 13.0, preferably between 2.0 and 10.0, and more preferably between 3.0 and 7.0, the glass can reduce the crystallization upper limit temperature and improve the ultraviolet transmittance and the irradiation resistance of the glass.
In some embodiments, when La2O3/Nb2O5When the value of (A) is controlled to be 3.5 to 15.0, preferably 5.0 to 14.0, more preferably 7.0 to 13.5, the glassThe ultraviolet radiation resistance and the glass stability are optimal.
Li2O、Na2O、K2O belongs to alkali metal oxide, and can reduce the high-temperature viscosity of the glass and provide free oxygen to reinforce the network structure of the glass, thereby improving the ultraviolet transmittance of the glass. At reasonable contents of Na from the viewpoint of the network structure of the consolidated glass2O and K2O is the strongest, but K2O is compared with Na2O has a greater ability to reduce the chemical stability of the glass, so that K is more strictly limited2The content of O. If Na2O and K2The content of O is too high, the volatilization of glass raw materials is serious in the production process, the stability of the refractive index is difficult to meet the design requirement, and the stability of the glass is poor. Therefore, Na is preferred2The content of O is 2-15%, more preferably 4-14%, and further preferably 5-13%; preferably K2The content of O is 0 to 8%, more preferably 1 to 6%, and further preferably 2 to 5%.
Li of alkali metal oxide2O has the strongest capacity of reducing high-temperature viscosity, and can contain a small amount of Li when the high-temperature viscosity design does not meet the requirement2However, if the content of O exceeds 5%, the glass is severely devitrified and the glass forming viscosity is low, so that it is difficult to satisfy the thick-gauge forming requirements. Thus, Li2The content of O is limited to 5% or less, preferably 4% or less, more preferably 3% or less, and further preferably Li is not contained2O。
In some embodiments of the invention, Li2O、Na2O、K2Total amount of O Li2O+Na2O+K2If O is lower than 3%, the temperature coefficient of the refractive index of the glass is rapidly increased, the refractive index of the glass lens is greatly changed under the condition of the same temperature change amplitude, and the imaging quality of the optical system is rapidly reduced; on the other hand, glass cannot achieve a good bubble degree. If Li2O+Na2O+K2The O content is more than 15 percent, the stability of the glass is rapidly reduced, the structure of the glass tends to be relaxed, and the ultraviolet radiation resistance is reduced. Therefore, Li is preferable2O+Na2O+K2O is 3 to 15%, more preferably 5 to 14%, and more preferably 6 to 13%.
A small amount of F (fluorine) can improve the ultraviolet transmittance and the ultraviolet radiation resistance of the glass. If the content of F exceeds 3%, the volatilization is large in the glass melting process, the fluctuation of the glass refractive index is brought, the optical uniformity of the glass is difficult to reach the design requirement, and meanwhile, the harm is brought to the production environment and the body health of operators. Therefore, the content of F is controlled to be 3% or less, preferably 2% or less, and more preferably 1% or less. In some embodiments, it is further preferred that the glass does not contain F if the glass has a sufficient UV transmittance and UV resistance.
In the invention, 0-1% of Sb is contained2O3、SnO、SnO2、CeO2One or more of Cl and Br is used as a clarifying agent, so that the clarifying effect of the glass can be improved, and the content of the clarifying agent is preferably 0-0.8%, and more preferably 0-0.5%. Preferably, the clarifying agent is Sb2O3When Sb is present2O3When the content exceeds 1%, the ultraviolet transmittance of the glass is lowered.
< component which should not be contained >
In the glass of the present invention, even when a small amount of oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo is contained singly or in combination, the glass is colored and absorbs at a specific wavelength in the visible light region, thereby impairing the property of the present invention to improve the effect of visible light transmittance.
In recent years, oxides of Th, Cd, Tl, Os, Be, and Se tend to Be used as harmful chemical substances in a controlled manner, and measures for protecting the environment are required not only in the glass production process but also in the processing process and disposal after commercialization. Therefore, when importance is attached to the influence on the environment, it is preferable that these components are not substantially contained except for inevitable mixing. Thus, the ultraviolet-transmitting glass becomes practically free from substances contaminating the environment. Therefore, the ultraviolet-transmitting glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental countermeasures.
To achieve environmental friendliness, the UV-transparent glasses of the invention preferably do not contain As2O3And PbO.
"0%" or "0%" is not included in the present invention, and means that the compound, molecule, element or the like is not intentionally added to the ultraviolet-transmitting glass of the present invention as a raw material; however, it is within the scope of the present invention that certain impurities or components, which are not intentionally added, may be present as raw materials and/or equipment for producing the uv-transparent glass and may be present in small or trace amounts in the final uv-transparent glass.
The properties of the ultraviolet-transmitting glass of the present invention will be described below.
< refractive index and Abbe number >
Refractive index (n) of glassd) And Abbe number (v)d) The test was carried out according to the method specified in GB/T7962.1-2010.
In some embodiments, the refractive index (n) of the glasses of the inventiond) The lower limit of (2) is 1.51, preferably 1.52, more preferably 1.53. In some embodiments, the refractive index (n) of the glasses of the inventiond) The upper limit of (b) is 1.58, preferably the upper limit is 1.57, and more preferably the upper limit is 1.56.
In some embodiments, the Abbe number (v) of the glasses of the inventiond) The lower limit of (2) is 55, preferably 56, more preferably 57. In some embodiments, the Abbe number (v) of the glasses of the inventiond) The upper limit of (2) is 65, preferably 63, more preferably 60.
< 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.
In some embodiments, the stability to water action of the glasses of the invention (D)W) Is 2 or more, preferably 1.
< stability against acid Effect >
Stability of the acid resistance of the glass (D)A) (powder method) according to the rule of GB/T17129And testing by a fixed method.
In some embodiments, the glass of the present invention is stable against acid action (D)A) Is 3 or more, preferably 2 or more, and more preferably 1.
< temperature coefficient of refractive index >
Temperature coefficient of refractive index (dn/dt) of glass the temperature coefficient of refractive index (d-line dn/dtrelative (10)) of glass at 40-60 ℃ was measured according to the method prescribed in GB/T7962.4-2010-6/℃))
In some embodiments, the temperature coefficient of refractive index (dn/dt) of the glasses of the invention is 8.0 × 10-6Preferably 7.0X 10 or less/° C-6Lower than/° C, more preferably 6.0X 10-6Below/° c.
<Internal transmittance tau at 365nm365nm>
The ultraviolet transmittance of the glass is characterized by the internal transmittance at 365nm and the internal transmittance at 365nm (tau)365nm) The thickness of the glass sample was 10mm as measured according to the method specified in GB/T7962.12-2010.
In some embodiments, the glass of the present invention has an internal transmittance (τ) at 365nm365nm) Is 99.0% or more, preferably 99.2% or more, more preferably 99.4% or more, and further preferably 99.5% or more.
<365nm internal transmittance ultraviolet radiation attenuation resistance >
Delta tau for ultraviolet radiation resistance of glass365nmCharacterizing that the transmittance at 365nm is resistant to ultraviolet radiation attenuation, and the test method comprises the following steps: the original internal transmittance tau of the sample at 365nm is tested according to the method specified in GB/T7962.12-2010365nm-1Irradiating with high-pressure mercury lamp to obtain glass with surface power density of 1W/cm2After 2 hours of irradiation, the internal transmittance at 365nm, τ, was again measured according to the method specified in GB/T7962.12-2010365nm-2Difference of two tests τ365nm-1-τ365nm-2I.e. the attenuation of the glass at this wavelength, the thickness of the glass sample was 10 mm.
In some embodiments, the glass of the present invention has an internal transmittance at 365nm that is resistant to attenuation by ultraviolet radiationEnergy (Delta tau)365nm) Is 5.0% or less, preferably 2.0% or less, and more preferably 1.0% or less.
< upper limit temperature of crystallization >
The crystallization performance of the glass is measured by adopting a gradient temperature furnace method, the glass is made into a sample of 180mm multiplied by 1mm0 multiplied by 10mm, the side surface is polished, the sample is put into a furnace with a temperature gradient (10 ℃/cm) to be heated to the temperature of the highest temperature zone of 1400 ℃, the sample is taken out after heat preservation is carried out for 4 hours and is naturally cooled to the room temperature, the crystallization condition of the glass is observed under a microscope, and the highest temperature corresponding to the occurrence of crystals of the glass is the crystallization upper limit temperature of the glass.
In some embodiments, the upper crystallization temperature limit of the glass of the present invention is 1300 ℃ or less, preferably 1280 ℃ or less, more preferably 1250 ℃ or less, and even more preferably 1230 ℃ or less.
< degree of bubbling >
The bubble degree of the glass was measured and classified according to the method prescribed in GB/T7962.8-2010.
In some embodiments, the glass of the present invention has a bubble size of class A or greater, preferably A0More preferably A or more00And (4) stages.
< degree of striae >
The streak degree test method of the glass is as follows: a striping machine was constructed with a point source and lenses, and the stripes were compared with the standard samples from the direction in which they were most easily seen, and were divided into four stages as specified in Table 1.
TABLE 1 stripiness grading Standard
| Rank of | Degree of streaking |
| A | No visible streaks under defined detection conditions |
| B | Has fine and dispersed stripes under specified conditions |
| C | Slight parallel stripes under specified conditions |
| D | Rough parallel stripes downstream of specified conditions |
In some embodiments, the glass of the present invention has a striae of grade C or greater, preferably grade B or greater.
< optical uniformity >
Optical homogeneity of glass is determined by the maximum value of refractive index deviation Deltan of each part in a glass sampledThe test is shown to be carried out according to the test method specified in GB/T7962.2-2010.
In some embodiments, Δ n for glasses of the inventiondValue of 5X 10-6Hereinafter, 3 × 10 is preferable-6Hereinafter, more preferably 2 × 10-6The following.
[ method for producing ultraviolet-transmitting glass ]
The manufacturing method of the ultraviolet-transmitting glass comprises the following steps: the glass is produced by adopting conventional raw materials and conventional processes, carbonate, nitrate, sulfate, hydroxide, oxide and the like are used as raw materials, the prepared furnace burden is put into a smelting furnace (such as a platinum crucible, a quartz crucible and the like) at 1200-1600 ℃ to be smelted after being proportioned according to the conventional method, and homogeneous molten glass without bubbles and undissolved substances is obtained after clarification, stirring and homogenization, and the molten glass is cast in a mold and annealed. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.
Glass preform and optical element
The glass preform can be produced from the produced ultraviolet-transmitting glass by means of direct gob casting, grinding, or press molding such as hot press molding. That is, the glass preform can be produced by direct precision gob-casting of a molten ultraviolet-transmitting glass into a glass precision preform, or by mechanical processing such as grinding and polishing, or by producing a preform for press molding from an ultraviolet-transmitting glass, reheat-press-molding the preform, and then polishing the preform. It should be noted that the means for producing the glass preform is not limited to the above means.
As described above, the ultraviolet-transmitting glass of the present invention is useful for various optical elements and optical designs, and among them, it is particularly preferable to form a preform from the ultraviolet-transmitting glass of the present invention, and use the preform to perform reheat press molding, precision press molding, or the like to manufacture optical elements such as lenses and prisms.
The glass preform and the optical element of the present invention are each formed of the ultraviolet-transmitting glass of the present invention described above. The glass prefabricated member has excellent characteristics of ultraviolet-transmitting glass; the optical element of the present invention has excellent characteristics of ultraviolet-transmitting glass, and can provide optical elements such as various lenses and prisms having high optical values.
Examples of the lens include various lenses such as a concave meniscus lens, a convex meniscus lens, a double convex lens, a double concave lens, a plano-convex lens, and a plano-concave lens, each of which has a spherical or aspherical lens surface.
[ optical instruments ]
The optical element formed by the ultraviolet-transmitting glass can be used for manufacturing optical instruments such as photographic equipment, camera equipment, projection equipment, display equipment, photoetching machines, vehicle-mounted equipment, monitoring equipment and the like.
Examples
< example of ultraviolet-transmitting glass >
In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.
In this example, the ultraviolet-transmitting glasses having the compositions shown in tables 2 to 3 were obtained by the above-described method for producing ultraviolet-transmitting glasses. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 2 to 3.
Table 2.
Table 3.
< glass preform example >
Various lenses such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses and plano-concave lenses, and preforms such as prisms were produced from the glasses obtained in examples 1 to 13 of ultraviolet-transmitting glasses by means of, for example, grinding or press molding such as reheat press molding and precision press molding.
< optical element example >
The preforms obtained from the above glass preform examples were annealed to reduce the internal stress of the glass and to fine-tune the refractive index so that the optical properties such as refractive index reached the desired values.
Next, each preform is ground and polished to produce various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens, and prisms. The surface of the resulting optical element may be coated with an antireflection film.
< optical Instrument example >
The optical element produced by the above-described optical element embodiments can be used, for example, for imaging devices, sensors, microscopes, medical technology, digital projection, communication, optical communication technology/information transmission, optics/illumination in the automotive field, lithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, by optical design, by forming an optical component or optical assembly using one or more optical elements.
Claims (13)
1. Ultraviolet-transmitting glass, characterized in that the components thereof, expressed in weight percent, comprise: SiO 22：55～70％；B2O3：2～18％；ZnO：1～20％；La2O3+Y2O3+Gd2O3：4～30％；Ta2O5+Nb2O5+TiO2+ZrO2：0.5～20％；Li2O+Na2O+K2O: 3 to 15% of (La)2O3+Y2O3+Gd2O3)/B2O30.3 to 6.0.
2. The uv-transparent glass according to claim 1, further comprising, in weight percent: BaO + SrO + CaO + MgO: 0 to 15 percent; and/or Al2O3: 0 to 5 percent; and/or F: 0 to 3 percent; and/or a clarifying agent: 0-1% of a clarifying agent Sb2O3、SnO、SnO2、CeO2One or more of Cl and Br.
3. UV-transmitting glass, characterized in that it contains SiO2、B2O3ZnO and alkali metal oxide as essential components, wherein the components comprise 4-30 wt% of La2O3+Y2O3+Gd2O3Wherein (La)2O3+Y2O3+Gd2O3)/B2O30.3 to 6.0, the ultraviolet-transmitting glassRefractive index n of glassd1.51 to 1.58, Abbe number vdIs 55 to 65, tau365nmIs more than 99.0%.
4. The UV-transparent glass according to claim 3, wherein the composition comprises, in weight percent: SiO 22: 55-70%; and/or B2O3: 2-18%; and/or ZnO: 1-20%; and/or Ta2O5+Nb2O5+TiO2+ZrO2: 0.5-20%; and/or Li2O+Na2O+K2O: 3-15%; and/or BaO + SrO + CaO + MgO: 0 to 15 percent; and/or Al2O3: 0 to 5 percent; and/or F: 0 to 3 percent; and/or a clarifying agent: 0-1% of a clarifying agent Sb2O3、SnO、SnO2、CeO2One or more of Cl and Br.
5. The UV-transparent glass according to any one of claims 1 to 4, wherein the composition thereof, expressed in weight percent, satisfies one or more of the following 6 conditions:
1)(La2O3+Y2O3+Gd2O3)/(Ta2O5+Nb2O5+TiO2+ZrO2) 1.0 to 13.0, preferably (La)2O3+Y2O3+Gd2O3)/(Ta2O5+Nb2O5+TiO2+ZrO2) 2.0 to 10.0, more preferably (La)2O3+Y2O3+Gd2O3)/(Ta2O5+Nb2O5+TiO2+ZrO2) 3.0 to 7.0;
2)La2O3/Nb2O5is 3.5 to 15.0, preferably La2O3/Nb2O55.0 to 14.0, more preferably La2O3/Nb2O57.0 to 13.5;
3)(La2O3+Y2O3+Gd2O3)/SiO20.07 to 0.35, preferably (La)2O3+Y2O3+Gd2O3)/SiO20.08 to 0.3, more preferably (La)2O3+Y2O3+Gd2O3)/SiO20.1 to 0.25;
4)(B2O3+Al2O3)/SiO20.05 to 0.4, preferably (B)2O3+Al2O3)/SiO20.08 to 0.35, more preferably (B)2O3+Al2O3)/SiO20.1 to 0.3;
5)(BaO+SrO+CaO+MgO)/SiO20.01 to 0.25, preferably (BaO + SrO + CaO + MgO)/SiO20.02 to 0.2, more preferably (BaO + SrO + CaO + MgO)/SiO20.02 to 0.1;
6)(La2O3+Y2O3+Gd2O3)/B2O30.4 to 5.0, preferably (La)2O3+Y2O3+Gd2O3)/B2O30.5 to 3.0.
6. The UV-transparent glass according to any one of claims 1 to 4, wherein the composition comprises, in weight percent: SiO 22: 56-68%, preferably SiO2: 57-67%; and/or B2O3: 4 to 16%, preferably B2O3: 5-15%; and/or ZnO: 2-16%, preferably ZnO: 3-12%; and/or La2O3+Y2O3+Gd2O3: 5 to 20%, preferably La2O3+Y2O3+Gd2O3: 7-15%; and/or Ta2O5+Nb2O5+TiO2+ZrO2: 1 to 15%, preferably Ta2O5+Nb2O5+TiO2+ZrO2: 2-10%; and/or Li2O+Na2O+K2O: 5 to 14%, preferably Li2O+Na2O+K2O: 6-13%; and/or BaO + SrO + CaO + MgO: 1-15%, preferably BaO + SrO + CaO + MgO: 1.5-10%, more preferably BaO + SrO + CaO + MgO: 1.5-8%; and/or Al2O3: 0 to 4%, preferably Al2O3: 0 to 3 percent; and/or F: 0-2%, preferably F: 0 to 1 percent; and/or a clarifying agent: 0-0.8%, preferably clarifying agent: 0-0.5%, the clarifying agent is Sb2O3、SnO、SnO2、CeO2One or more of Cl and Br.
7. The UV-transparent glass according to any one of claims 1 to 4, wherein the composition comprises, in weight percent: la2O3: 4-25%, preferably La2O3: 6 to 20%, more preferably La2O3: 7-14%; and/or Gd2O3: 0 to 8%, preferably Gd2O3: 0 to 7%, more preferably Gd2O3: 0 to 5 percent; and/or Y2O3: 0 to 10%, preferably Y2O3: 0 to 8%, more preferably Y2O3: 0 to 5 percent; and/or Na2O: 2-15%, preferably Na2O: 4 to 14%, more preferably Na2O: 5-13%; and/or K2O: 0 to 8%, preferably K2O: 1 to 6%, more preferably K2O: 2-5%; and/or Li2O: 0 to 5%, preferably Li2O: 0 to 4%, more preferably Li2O：0～3％。
8. The UV-transparent glass according to any one of claims 1 to 4, wherein the UV-transparent glass has a refractive index nd1.51 to 1.58, preferably 1.52 to 1.57, more preferably 1.53 to 1.56, and/or an Abbe number vdIs 55 to 65, preferably 56 to 63, and more preferably 57 to 60.
9. The UV-transparent glass according to any one of claims 1 to 4, wherein the glass is characterized byTau of said UV-transparent glass365nm99.0% or more, preferably 99.2% or more, more preferably 99.4% or more, still more preferably 99.5% or more, and/or Δ τ365nmIs 5.0% or less, preferably 2.0% or less, and more preferably 1.0% or less.
10. The UV-transparent glass according to any one of claims 1 to 4, wherein the UV-transparent glass has a water-resistant stability DWIs 2 or more, preferably 1; and/or stability against acid action DAIs 3 or more, preferably 2 or more, more preferably 1; and/or a temperature coefficient of refractive index dn/dt of 8.0 x 10-6Preferably 7.0X 10 or less/° C-6Lower than/° C, more preferably 6.0X 10-6Below/° c; and/or the upper limit temperature of crystallization is 1300 ℃ or lower, preferably 1280 ℃ or lower, more preferably 1250 ℃ or lower, and still more preferably 1230 ℃ or lower; and/or the degree of bubbling is class A or more, preferably class A0More preferably A or more00A stage; and/or the degree of streaking is at least level C, preferably at least level B; and/or Δ ndValue of 5X 10-6Hereinafter, 3 × 10 is preferable-6Hereinafter, more preferably 2 × 10-6The following.
11. A glass preform, characterized by being made of the ultraviolet-transmitting glass according to any one of claims 1 to 10.
12. An optical element, characterized in that it is made of the ultraviolet-transmitting glass according to any one of claims 1 to 10 or the glass preform according to claim 11.
13. An optical device comprising the ultraviolet-transmitting glass according to any one of claims 1 to 10 and/or comprising the optical element according to claim 12.
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| CN115180825A (en) * | 2022-08-09 | 2022-10-14 | 中建材玻璃新材料研究院集团有限公司 | Ultraviolet high-transparency glass suitable for float forming and preparation method thereof |
| CN115180825B (en) * | 2022-08-09 | 2023-10-10 | 中建材玻璃新材料研究院集团有限公司 | Ultraviolet high-transmittance glass suitable for float forming and preparation method thereof |
| CN117550804A (en) * | 2024-01-11 | 2024-02-13 | 上海罗金光电科技有限公司 | Low-cost ultraviolet-transmitting lamp tube glass and annealing process thereof |
| CN117550804B (en) * | 2024-01-11 | 2024-03-19 | 上海罗金光电科技有限公司 | Low-cost ultraviolet-transmitting lamp tube glass and annealing process thereof |
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