CN112047625A - Ultraviolet-transmitting optical glass - Google Patents

Ultraviolet-transmitting optical glass Download PDF

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Publication number
CN112047625A
CN112047625A CN202010981999.8A CN202010981999A CN112047625A CN 112047625 A CN112047625 A CN 112047625A CN 202010981999 A CN202010981999 A CN 202010981999A CN 112047625 A CN112047625 A CN 112047625A
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China
Prior art keywords
ultraviolet
optical glass
transmitting optical
glass
sio
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CN202010981999.8A
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CN112047625B (en
Inventor
郝良振
孙伟
毛露路
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CDGM Glass Co Ltd
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CDGM Glass Co Ltd
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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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • 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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

The invention provides ultraviolet-transmitting optical glass, which comprises the following components in percentage by mole: SiO 22：55～75％；Al2O3：1～10％；B2O3：5～20％；Li2O+Na2O+K2O: 5 to 30% of SiO2/(Li2O+Na2O+K2O) is 2.0 to 15.0. By reasonably designing the content of each component, the glass obtained by the invention has the characteristics of low transition temperature, excellent chemical stability, high ultraviolet transmittance and the like.

Description

Ultraviolet-transmitting optical glass
Technical Field
The invention relates to optical glass, in particular to ultraviolet-transmitting optical glass.
Background
Compared with the traditional ultraviolet mercury lamp light source, the ultraviolet light emitting diode has the characteristics of high luminous efficiency, quick response, low cost and the like, and is widely applied to the fields of medical cosmetology, sterilization, disinfection, ultraviolet detection and the like. In order to protect the LED chip and improve the light emitting efficiency, a layer of uv-transparent material is usually packaged on the surface of the LED chip. Organic glue is a commonly used ultraviolet-transmitting material, but the organic glue has poor chemical stability and is easy to cause poor packaging air tightness due to corrosion after long-time use. In addition, the problem of transmittance attenuation of the organic glue under ultraviolet irradiation can cause the reduction of the luminous efficiency of the LED. The ultraviolet transmitting glass is an excellent ultraviolet transmitting window material due to the characteristics of good ultraviolet transmitting performance, excellent chemical stability, adjustable linear expansion coefficient and the like.
CN106977096A discloses an optical glass with high ultraviolet band transmittance and ultraviolet radiation resistance, but the optical glass contains 60-70% of phosphoric acid and 13-15% of boric acid by mass percent, the chemical stability of the glass is poor, and the durability of the glass can be affected when the glass is used as an ultraviolet transmission window material.
Disclosure of Invention
The invention aims to provide ultraviolet-transmitting optical glass with excellent chemical stability.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(1) the ultraviolet-transmitting optical glass comprises the following components in percentage by mole: SiO 22：55～75％；Al2O3：1～10％；B2O3：5～20％；Li2O+Na2O+K2O: 5 to 30% of SiO2/(Li2O+Na2O+K2O) is 2.0 to 15.0.
(2) The ultraviolet-transmitting optical glass comprises the following components in percentage by mole: SiO 22：55～75％；Al2O3+B2O3：10～27％，Li2O+Na2O+K2O: 5 to 30% of SiO2/(Li2O+Na2O+K2O) is 2.0-15.0, and the transmittance tau of the ultraviolet transmitting optical glass280nmIs 0.75 or more.
(3) The ultraviolet-transmitting optical glass according to any one of (1) and (2), which further comprises, in terms of mole percent: and (3) RO: 0 to 10 percent; and/or ZnO: 0 to 5 percent; and/or ZrO2: 0-5%, wherein the RO is one or more of MgO, CaO, SrO and BaO.
(4) UV-transmitting optical glass, the composition of which is expressed in mole percent and is made of SiO2：55～75％；Al2O3：1～10％；B2O3：5～20％；Li2O+Na2O+K2O：5～30％；RO：0～10％；ZnO：0～5％；ZrO2: 0 to 5% of SiO2/(Li2O+Na2O+K2O) is 2.0-15.0, and the RO is one or more of MgO, CaO, SrO and BaO.
(5) The ultraviolet-transmitting optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: li2O+Na2O+K2O is 10 to 25%, preferably Li2O+Na2O+K2O is 12 to 22%.
(6) The ultraviolet-transmitting optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: 5K2O+4Na2O+2.5Li2O is 40-70%, preferably 5K2O+4Na2O+2.5Li2O is 43 to 65%, more preferably 5K2O+4Na2O+2.5Li2The content of O is 45-60%.
(7) The ultraviolet-transmitting optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: SiO 22+Al2O360 to 80%, preferably SiO2+Al2O363 to 76%, and SiO is more preferable2+Al2O3Is 66 to 74 percent.
(8) The ultraviolet-transmitting optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: al (Al)2O3/B2O30.1 to 1.6, preferably Al2O3/B2O30.2 to 1.0, more preferably Al2O3/B2O30.25 to 0.6.
(9) The ultraviolet-transmitting optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: SiO 22/B2O33.0 to 13.5, preferably SiO2/B2O33.5 to 10.0, more preferably SiO2/B2O3Is 4.0 to 7.0.
(10) The ultraviolet-transmitting optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: al (Al)2O3+B2O310 to 27%, preferably Al2O3+B2O312 to 25%, more preferably Al2O3+B2O3Is 14 to 22%.
(11) The ultraviolet-transmitting optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: SiO 22/(Li2O+Na2O+K2O) is 2.5 to 10.0, preferably SiO2/(Li2O+Na2O) is 3.0 to 8.0.
(12) The ultraviolet-transmitting optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: SiO 22: 60-70%, preferably SiO2: 62-68%; and/or Al2O3: 2-8%, preferably Al2O3: 3-7%; and/or B2O3: 8 to 18%, preferably B2O3: 10-16%; and/or Li2O: 0 to 25%, preferably Li2O: 5 to 20%, more preferably Li2O: 11-18%; and/or Na2O: 0 to 10%, preferably Na2O: 1 to 8%, more preferably Na2O: 2-6%; and/or K2O: 0 to 10%, preferably K2O: 0 to 5%, more preferably K2O: 0-2%; and/or RO: 0-8%, preferably RO: 0 to 5 percent; and/or ZnO: 0-2%; and/or ZrO2: 0-2%, and the RO is one or more of MgO, CaO, SrO and BaO.
(13) The ultraviolet-transmitting optical glass according to any one of (1) to (3), which further comprises, in terms of weight percent: f: 0 to 1 percent.
(14) The ultraviolet-transmitting optical glass according to any one of (1) to (4), wherein SnO is not contained in the composition; and/or does not contain P2O5(ii) a And/or does not contain RO; and/or does not contain K2O; and/or no ZnO; and/or does not contain ZrO2(ii) a And/or does not contain F; and/or does not contain CeO2(ii) a And/or does not contain Ln2O3RO is one or more of MgO, CaO, SrO and BaO, Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
(15) The ultraviolet-transmitting optical glass according to any one of (1) to (4), wherein the transition temperature T of the ultraviolet-transmitting optical glassg520 ℃ or lower, preferably 510 ℃ or lower, more preferably 500 ℃ or lower; and/or the linear expansion coefficient alpha of the ultraviolet-transmitting optical glass is 60 multiplied by 10-7/K～75×10-7Preferably 62X 10,/K-7/K～72×10-7More preferably 63X 10,/K-7/K～70×10-7K; and/or the stability to water of UV-transmitting optical glass DWIs 2 or more, preferably 1; and/or stability of the acid-resistance of the UV-transmitting optical glass DAIs 2 or more, preferably 1; and/or the transmittance tau of the ultraviolet-transmitting optical glass280nm0.75 or more, preferably 0.78 or more, more preferably 0.80 or more; and/or refractive index n of ultraviolet-transmitting optical glassd1.47 to 1.54, preferably 1.49 to 1.53, more preferably 1.50 to 1.525; and/or Abbe number v of ultraviolet-transmitting optical glassdIs 62 to 68, preferably 63 to 67, and more preferably 63 to 66.
(16) A package member made of the ultraviolet-transmitting optical glass according to any one of (1) to (15).
(17) A glass preform characterized by being made of the ultraviolet-transmitting optical glass according to any one of (1) to (15).
(18) An optical element produced from the ultraviolet-transmitting optical glass according to any one of (1) to (15) or the glass preform according to (17).
(19) An optical device comprising the ultraviolet-transmitting optical glass according to any one of (1) to (15) and/or the optical element according to (18).
The invention has the beneficial effects that: by reasonably designing the content of each component, the glass obtained by the invention has the characteristics of low transition temperature, excellent chemical stability, high ultraviolet transmittance and the like.
In some embodiments, the resulting glass has a linear expansion coefficient of 60 × 10-7/K～75×10-7and/K, being applicable to the fields of ceramic packaging and the like.
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 invention is not limited thereto, and the ultraviolet-transmitting optical glass of the present invention may be simply referred to as optical glass or glass in the following description.
[ ultraviolet-transmitting optical glass ]
The ranges of the respective components (components) of the ultraviolet-transmitting optical glass of the present invention are explained below. In the present invention, unless otherwise specified, the contents and total contents of the respective components are all expressed in terms of mole percent (mol%), that is, the contents and total contents of the respective components are expressed in terms of mole percent relative to the total amount of glass matter converted into the composition of oxides. Here, the term "composition in terms of oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the optical glass composition component of the present invention are decomposed in the melt and converted into oxides, the total molar 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 >
SiO2The ultraviolet cut absorption wavelength of (2) is 160nm, is a high-quality ultraviolet-transmitting material, and is an essential component and a network former of the glass. In addition, SiO2The quartz sand as the main raw material can achieve very high purity, can reduce the introduction of impurities when used as a raw material of the ultraviolet-transmitting glass, and is more favorable for obtaining the optical glass with high ultraviolet band transmittance. When SiO is present2When the content of (A) is less than 55%, the ultraviolet transmittance of the glass is remarkably reduced, and when SiO is contained in the glass2Of (1) containsAbove 75%, the glass becomes difficult to melt. Thus, SiO2The content of (B) is 55 to 75%, preferably 60 to 70%, more preferably 62 to 68%.
Al2O3In the present invention, it is also a network former, and it may be bonded to Al on the surface of ceramics2O3The glass and the ceramic material are fused together, so that the wettability of the glass to the ceramic material is increased, and the connection between the glass and the ceramic material is firmer. On the other hand, Al2O3The glass can capture free oxygen in the glass, and the ultraviolet transmittance of the glass is improved. But Al2O3The linear expansion coefficient of the glass can be reduced, and when the content is too high, the linear expansion coefficient of the glass is too small, so that the risk of air leakage after packaging is increased. Therefore, Al in the present invention2O3The content of (b) is 1 to 10%, preferably 2 to 8%, more preferably 3 to 7%.
B2O3The ultraviolet cut-off absorption wavelength of the glass is 170nm, and the glass has the effects of reducing the material melting temperature and high-temperature viscosity and improving the glass production performance, and if B is B2O3The content of less than 5% does not sufficiently achieve the above effects, but if it exceeds 20%, the chemical stability of the glass is lowered. Thus, B2O3The content of (b) is 5 to 20%, preferably 8 to 18%, more preferably 10 to 16%.
RO (RO is one or more of MgO, CaO, SrO and BaO) has the effect of increasing the mechanical strength of the glass, but when the content is too large, the linear expansion coefficient of the glass becomes large, and the ultraviolet transmittance is deteriorated. In order to obtain excellent chemical stability and adjust the devitrification resistance and the linear expansion coefficient of the glass, the content of the alkaline earth metal oxide RO in the present invention is 0 to 10%, preferably 0 to 8%, more preferably 0 to 5%, and further preferably no RO.
The ZnO can adjust the refractive index and Abbe number of the glass and improve the water resistance of the glass, and the content of the ZnO is 0-5%, preferably 0-2%. From the viewpoint of enhancing the ultraviolet transmittance of the glass, it is more preferable that ZnO is not contained.
ZrO2Can increase the mechanical strength and hardness of the glassDevitrification resistance of glass liter, but ZrO2The melting is difficult, and the material melting is difficult when the content is too large. Thus, ZrO in the invention2Is 0 to 5%, preferably 0 to 2%, more preferably contains no ZrO2。
Li2O、Na2O、K2O belongs to alkali metal oxide, is a key component for adjusting the linear expansion coefficient of the glass, and is formed by reasonably designing Li2O、Na2O、K2The content of O can realize controllable adjustment of the linear expansion coefficient at a small cost. The alkali metal oxide has the other function of breaking the network structure of a glass former in the glass, reducing the high-temperature viscosity of the glass and enabling clarification and homogenization to be easier, thereby achieving the purpose of reducing the production difficulty of the glass, and simultaneously the obtained glass has lower transition temperature. In the present invention, Li2The content of O is 0 to 25%, preferably 5 to 20%, more preferably 11 to 18%. Na (Na)2The content of O is 0 to 10%, preferably 1 to 8%, more preferably 2 to 6%. K2The content of O is 0 to 10%, preferably 0 to 5%, more preferably 0 to 2%, and further preferably K is not contained2O。
Alkali metal oxides in glass increase the amount of "free oxygen" in the glass, making the glass less transparent to ultraviolet light. In order to ensure the ultraviolet transmission performance of the glass, the inventor finds that when Li is used in repeated experimental research2O、Na2O、K2O and total content Li2O+Na2O+K2When O is preferably within the range of 5-30%, the ultraviolet transmitting performance and the linear expansion coefficient of the glass can better meet the design requirements, and Li is more preferably used2O+Na2O+K2O is 10 to 25%, and Li is more preferable2O+Na2O+K2O is 12 to 22%.
In the present invention, Li2O、Na2O、K2O is an alkali metal oxide, but has a different influence on the linear expansion coefficient of the glass. As a result of the inventors' extensive research, it was found that in some embodiments, the alkali metal oxide content satisfied 5K2O+4Na2O+2.5Li2When the content of O is between 40 and 70 percent,the linear expansion coefficient of the obtained glass can better meet the design requirement. Preferably 5K2O+4Na2O+2.5Li2O is 43 to 65%, more preferably 5K2O+4Na2O+2.5Li2The content of O is 45-60%.
SiO2And Al2O3Has the function of improving the chemical stability of glass when being made of SiO2And Al2O3When the content is too high, the high-temperature viscosity of the glass is increased, and the productivity is reduced. In some embodiments of the invention, if SiO2And Al2O3SiO in total content2+Al2O3Above 80%, the bubble problem of the glass is difficult to solve, so that the bubble degree grade of the glass is low, and the production difficulty is obviously increased; if SiO2And Al2O3SiO in total content2+Al2O3If the amount is too low, the chemical stability of the glass does not meet the design requirements. Thus, SiO in the present invention2+Al2O3Preferably 60 to 80%, more preferably SiO2+Al2O363 to 76%, and SiO is more preferable2+Al2O3Is 66 to 74 percent.
The inventor researches and discovers that Al2O3And B2O3In the glass, the structure of the glass can be influenced by self-coordination change, and further, the linear expansion coefficient, the chemical stability, the transition temperature and the like of the glass are influenced. In some embodiments, when Al2O3And B2O3Ratio of (A) to (B) Al2O3/B2O3When the content is between 0.1 and 1.6, the glass has excellent chemical stability, lower transition temperature and proper linear expansion coefficient, and Al is preferred2O3/B2O30.2 to 1.0, more preferably Al2O3/B2O30.25 to 0.6.
The inventors have intensively studied to find that SiO is regulated2And B2O3Can effectively utilize B2O3To adjust the chemical stability and mechanical properties of the glassStrength, etc. In some embodiments, when SiO2And B2O3Ratio of (A) to (B) SiO2/B2O3When the content is between 3.0 and 13.5, the glass can obtain better chemical stability and mechanical strength. SiO is preferred2/B2O33.5 to 10.0, more preferably SiO2/B2O3Is 4.0 to 7.0.
In the present invention, Al2O3And B2O3Can capture free oxygen in the glass to improve the ultraviolet transmittance of the glass, and simultaneously, the introduction of the free oxygen and the ultraviolet transmittance can cause the linear expansion coefficient of the glass to be reduced. In some embodiments, to ensure that the linear expansion coefficient and the ultraviolet transmittance of the glass better meet the design requirements, Al2O3And B2O3Total content of Al2O3+B2O3Preferably 10 to 27%, more preferably 12 to 25%, and still more preferably 14 to 22%.
Through a large number of experimental researches, the proportion of free oxygen and combined oxygen in the glass is found to be a key factor influencing the ultraviolet transmittance. SiO 22The increase of the content can increase the proportion of the combined oxygen in the glass and improve the ultraviolet transmittance, and the increase of the alkali metal can reduce the proportion of the combined oxygen and reduce the ultraviolet transmittance of the glass. In some embodiments, when SiO2And the total content Li of the alkali metal oxide2O+Na2O+K2Ratio of O SiO2/(Li2O+Na2O+K2O) is in the range of 2.0 to 15.0, the glass can obtain high ultraviolet transmittance, and SiO is preferable2/(Li2O+Na2O+K2O) is 2.5 to 10.0, and SiO is more preferable2/(Li2O+Na2O+K2O) is 3.0 to 8.0.
In the present invention, part or all of the above-mentioned one or more oxide components may be replaced with a fluoride, such as NaF, AlF3、CaF2、K2SiF6、KHF2And the like. Fluorine (F) has the effects of reducing the high-temperature viscosity of the glass and improving the chemical stability of the glass, in particularImproving the acid resistance stability. Meanwhile, a small amount of fluorine can inhibit Fe impurity in the glass3+Coloring and improving the ultraviolet transmittance of the glass. But fluorine volatilizes in the glass packaging process, so that the packaging stability and the yield are influenced. On the other hand, the volatilization of fluorine in the smelting process has great damage to the health of operators and the environment. In the present invention, part or all of the above one or more oxide components are replaced with fluoride, and the total content of F element in fluoride is controlled to 0 to 1%, and preferably F is not contained.
In some embodiments of the present invention, it is preferred that SnO be absent in order to achieve excellent chemical stability of the glass. P2O5May result in a decrease in the chemical stability of the glass, and in addition P2O5It is preferable that P is not contained because silicate glass is generally used as a nucleating agent and the resistance to devitrification of the glass is deteriorated in silicate glass2O5. Due to the restriction of rare earth separation and purification technology, the rare earth oxide raw material often contains Er2O3、Nd2O3、Tm2O3And the like, which greatly affect the ultraviolet transmittance, and a small amount of the impurities causes a rapid deterioration in the ultraviolet transmittance of the glass, and thus, in some embodiments of the present invention, it is preferable that Ln is not contained2O3(Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of) and/or does not contain CeO2。TiO2Since iron-titanium mixed coloration is generated in the glass with iron impurities in the glass and affects the ultraviolet transmittance of the glass, TiO is preferably not contained in the present invention2。
< component which should not be contained >
In the glass of the present invention, oxides of Th, Cd, Tl, Os, Be and Se tend to Be used as harmful chemical substances in recent years, 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, in the case where the influence on the environment is emphasized, the influence is removedIt is preferable that they are not substantially contained except for the inevitable mixing. Thereby, the optical glass becomes practically free from substances contaminating the environment. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental countermeasures. In order to achieve environmental friendliness, the optical glass of the present invention preferably does not contain As2O3And PbO.
"0%" or "0%" is not contained in the present invention, and means that the compound, molecule, element or the like is not intentionally added as a raw material to the ultraviolet-transmitting optical glass of the present invention; 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 glass and may be present in small or trace amounts in the final uv-transparent optical glass.
Next, the performance of the ultraviolet-transmitting optical glass of the present invention will be explained.
< coefficient of linear expansion >
The coefficient of linear expansion (alpha) of the ultraviolet-transmitting optical glass is tested according to the method specified in GB/T7962.16-2010.
In some embodiments, the lower limit of the linear expansion coefficient (α) of the ultraviolet-transmitting optical glass is 60 × 10-7A preferred lower limit of 62X 10-7A more preferable lower limit is 63X 10-7/K。
In some embodiments, the upper limit of the linear expansion coefficient (α) of the ultraviolet-transmitting optical glass is 75 × 10-7Preferably, the upper limit is 72X 10-7More preferably, the upper limit is 70X 10-7/K。
< transition temperature >
Transition temperature (T) of ultraviolet-transmitting optical glassg) The test was carried out according to the method specified in GB/T7962.16-2010.
In some embodiments, the transition temperature (T) of the ultraviolet-transmissive optical glassg) Is 520 ℃ or lower, preferably 510 ℃ or lower, and more preferably 500 ℃ or lower.
< stability against Water action >
Stability to water action by UV-transparent optical glass powder method (DW) Measured using the GB/T17129 test standard.
In some embodiments, the UV-transparent optical glass has stability to water effects (D)W) Is 2 or more, preferably 1.
< stability against acid Effect >
Stability against acid action by UV-transmitting optical glass powder method (D)A) Measured using the GB/T17129 test standard.
In some embodiments, the stability of the ultraviolet-transmitting optical glass against acid effects (D)A) Is 2 or more, preferably 1.
< transmittance >
Transmittance (tau) of ultraviolet-transmitting optical glass280nm) The test method comprises the following steps: the glass sample was processed to 40X 30X 1mm3And two 40X 30mm2The surface was polished and then placed in a spectrophotometer to test the transmittance at 280nm of the glass.
In some embodiments, the transmittance (τ) of the ultraviolet-transmissive optical glass280nm) Is 0.75 or more, preferably 0.78 or more, and more preferably 0.80 or more.
< refractive index and Abbe number >
Refractive index (n) of ultraviolet-transmitting optical 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 ultraviolet-transmissive optical glassd) The lower limit of (b) is 1.47, preferably 1.49, more preferably 1.50.
In some embodiments, the refractive index (n) of the ultraviolet-transmissive optical glassd) The upper limit of (a) is 1.54, the preferred upper limit is 1.53, and the more preferred upper limit is 1.525.
In some embodiments, the abbe number (v) of the ultraviolet-transmitting optical glassd) The lower limit of (2) is 62, preferably the lower limit is 63.
In some embodiments, the abbe number (v) of the ultraviolet-transmitting optical glassd) The upper limit of (3) is 68, the upper limit is preferably 67, and the upper limit is more preferably 66.
[ method for producing ultraviolet-transmitting optical glass ]
The manufacturing method of the ultraviolet-transmitting optical glass comprises the following steps: the glass composition is prepared by uniformly mixing raw materials (for example, carbonate, nitrate, sulfate, hydroxide, oxide, fluoride, etc. can be used as raw materials), putting the uniformly mixed raw materials into a crucible within a predetermined content range, melting the raw materials at 1300 to 1500 ℃ for 2 to 5 hours according to the melting difficulty of the glass composition, stirring the raw materials to be homogenized, reducing the temperature to a proper temperature, casting the mixture into a mold, and slowly cooling the mold. 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 optical glass 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 ultraviolet-transmitting optical glass by grinding, polishing, or the like, or by producing a preform for press molding from the ultraviolet-transmitting optical glass, 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. As described above, the ultraviolet-transmitting optical 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 optical 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 optical glass of the present invention described above. The glass prefabricated member has excellent characteristics of ultraviolet-transmitting optical glass; the optical element of the present invention has excellent characteristics of ultraviolet-transmitting optical 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 ultraviolet-transmitting optical glass and the optical element formed by the ultraviolet-transmitting optical glass can be used for manufacturing optical instruments such as photographic equipment, vehicle-mounted equipment, camera equipment, display equipment, monitoring equipment, ultraviolet light-emitting diodes and the like.
[ packaging Member ]
The ultraviolet-transmitting optical glass can also be applied to the field of packaging. The invention also provides a packaging element which is manufactured by the ultraviolet-transmitting optical glass according to a method well known by a person skilled in the field of ceramic packaging.
Examples
< example of ultraviolet-transmitting optical glass >
In the following, the examples listed in the tables will describe the invention in more detail, for reference to other skilled persons. It should be noted that the glass component contents in examples 1 to 30 are expressed in terms of mole percent, and the scope of the present invention is not limited to the examples.
In this example, glasses having the structures shown in tables 1 to 3 were obtained by the above-mentioned method for producing ultraviolet-transmitting optical glass. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 3.
Table 1.
Figure BDA0002687865640000111
Figure BDA0002687865640000121
Table 2.
Example (mol%) 11 12 13 14 15 16 17 18 19 20
SiO2 61.95 65.24 67.12 60.24 62.75 62.61 60.25 64.24 60.14 66.99
Al2O3 8.51 7.06 2.41 4.40 5.14 6.54 8.54 3.27 5.21 4.58
B2O3 7.57 9.58 18.27 15.42 6.24 13.98 5.57 13.75 10.65 7.14
RO 3.24 1.27 0 1.24 6.57 0.54 3.22 0.26 1.21 1.15
ZnO 1.24 0 0 3.54 0.27 0.54 0 0.24 0 0
ZrO2 0 0 0 0 0 0 2.25 0 0 0
Li2O 10.24 16.85 0.41 4.65 14.24 10.25 11.52 18.24 22.41 20.14
Na2O 7.25 0 9.54 2.36 2.54 5.54 4.14 0 0.14 0
K2O 0 0 2.25 8.15 2.25 0 4.51 0 0.24 0
Total up to 100 100 100 100 100 100 100 100 100 100
(F) 0 0 (0.45) 0 0 0 (0.21) 0 (0.66) 0
Li2O+Na2O+K2O 17.49 16.85 12.20 15.16 19.03 15.79 20.17 18.24 22.79 20.14
5K2O+4Na2O+2.5Li2O 54.60 42.13 50.44 61.82 57.01 47.79 67.91 45.60 57.79 50.35
SiO2+Al2O3 70.46 72.30 69.53 64.64 67.89 69.15 68.79 67.51 65.35 71.57
Al2O3/B2O3 1.12 0.74 0.13 0.29 0.82 0.47 1.53 0.24 0.49 0.64
SiO2/B2O3 8.18 6.81 3.67 3.91 10.06 4.48 10.82 4.67 5.65 9.38
Al2O3+B2O3 16.08 16.64 20.68 19.82 11.38 20.52 14.11 17.02 15.86 11.72
SiO2/(Li2O+Na2O+K2O) 3.54 3.87 5.50 3.97 3.30 3.97 2.99 3.52 2.64 3.33
α(×10-7/K) 65 62 63 68 66 62 70 61 67 63
Tg(℃) 508 500 520 516 502 495 511 503 475 474
Dw Class 1 Class 1 Class 1 Class 1 Class 1 Class 1 Class 2 Class 1 Class 2 Class 2
DA Class 1 Class 1 Class 1 Class 2 Class 1 Class 1 Class 1 Class 1 Class 2 Class 2
τ280nm 0.80 0.85 0.77 0.81 0.86 0.82 0.80 0.77 0.82 0.80
nd 1.53675 1.49852 1.50365 1.53254 1.51903 1.48354 1.50254 1.53987 1.49325 1.50124
vd 64.21 64.21 65.87 65.87 66.54 66.02 65.25 67.87 62.78 63.45
Table 3.
Figure BDA0002687865640000122
Figure BDA0002687865640000131
< packaging component embodiment >
The ultraviolet-transmitting optical glass obtained in examples 1 to 10 was processed into a predetermined size, and at a sealing temperature, a ceramic base, a case, a lead, a frame, and the like were sealed by the ultraviolet-transmitting optical glass into a single body according to a certain temperature profile and a sintering atmosphere, thereby obtaining a package element.
< 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 by using glasses obtained from examples 11 to 20 of ultraviolet-transmitting optical glasses by means of polishing 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 (19)

1. Ultraviolet-transmitting optical glass, characterized in that its components, expressed in mole percent, contain: SiO 22：55～75％；Al2O3：1～10％；B2O3：5～20％；Li2O+Na2O+K2O: 5 to 30% of SiO2/(Li2O+Na2O+K2O) is 2.0 to 15.0.
2. Ultraviolet-transmitting optical glass, characterized in that its components, expressed in mole percent, contain: SiO 22：55～75％；Al2O3+B2O3：10～27％，Li2O+Na2O+K2O: 5 to 30% of SiO2/(Li2O+Na2O+K2O) is 2.0-15.0, and the transmittance tau of the ultraviolet transmitting optical glass280nmIs 0.75 or more.
3. The uv-transparent optical glass according to any one of claims 1 or 2, further comprising, in mole percent: and (3) RO: 0 to 10 percent; and/or ZnO: 0 to 5 percent; and/or ZrO2: 0-5%, wherein the RO is one or more of MgO, CaO, SrO and BaO.
4. UV-transparent optical glass, characterized in that its composition, expressed in mole percentage, is represented by SiO2：55～75％；Al2O3：1～10％；B2O3：5～20％；Li2O+Na2O+K2O：5～30％；RO：0～10％；ZnO：0～5％；ZrO2: 0 to 5% of SiO2/(Li2O+Na2O+K2O) is 2.0-15.0, and the RO is one or more of MgO, CaO, SrO and BaO.
5. The ultraviolet-transmitting optical glass according to any one of claims 1 to 4, wherein the composition is represented by weight percentage, wherein: li2O+Na2O+K2O is 10 to 25%, preferably Li2O+Na2O+K2O is 12 to 22%.
6. The ultraviolet-transmitting optical glass according to any one of claims 1 to 4, wherein the composition is represented by weight percentage, wherein: 5K2O+4Na2O+2.5Li2O is 40-70%, preferably 5K2O+4Na2O+2.5Li2O is 43 to 65%, more preferably 5K2O+4Na2O+2.5Li2The content of O is 45-60%.
7. The ultraviolet-transmitting optical glass according to any one of claims 1 to 4, wherein the composition is represented by weight percentage, wherein: SiO 22+Al2O360 to 80%, preferably SiO2+Al2O363 to 76%, and SiO is more preferable2+Al2O3Is 66 to 74 percent.
8. The ultraviolet-transmitting optical glass according to any one of claims 1 to 4, wherein the composition is represented by weight percentage, wherein: al (Al)2O3/B2O30.1 to 1.6, preferably Al2O3/B2O30.2 to 1.0, more preferably Al2O3/B2O30.25 to 0.6.
9. The ultraviolet-transmitting optical glass according to any one of claims 1 to 4, wherein the composition is represented by weight percentage, wherein: SiO 22/B2O33.0 to 13.5, preferably SiO2/B2O33.5 to 10.0, more preferably SiO2/B2O3Is 4.0 to 7.0.
10. The ultraviolet-transmitting optical glass according to any one of claims 1 to 4, wherein the composition is represented by weight percentage, wherein: al (Al)2O3+B2O310 to 27%, preferably Al2O3+B2O312 to 25%, more preferably Al2O3+B2O3Is 14 to 22%.
11. The ultraviolet-transmitting optical glass according to any one of claims 1 to 4, wherein the composition is represented by weight percentage, wherein: SiO 22/(Li2O+Na2O+K2O) is 2.5 to 10.0, preferably SiO2/(Li2O+Na2O) is 3.0 to 8.0.
12. The ultraviolet-transmitting optical glass according to any one of claims 1 to 4, wherein the composition is represented by weight percentage, wherein: SiO 22: 60-70%, preferably SiO2: 62-68%; and/or Al2O3: 2-8%, preferably Al2O3: 3-7%; and/or B2O3: 8 to 18%, preferably B2O3: 10-16%; and/or Li2O: 0 to 25%, preferably Li2O: 5 to 20%, more preferably Li2O: 11-18%; and/or Na2O: 0 to 10%, preferably Na2O: 1 to 8%, more preferably Na2O: 2-6%; and/or K2O: 0 to 10%, preferably K2O: 0 to 5%, more preferably K2O: 0-2%; and/or RO: 0-8%, preferably RO: 0 to 5 percent; and/or ZnO: 0-2%; and/or ZrO2: 0-2%, and the RO is one or more of MgO, CaO, SrO and BaO.
13. The ultraviolet-transmitting optical glass according to any one of claims 1 to 3, further comprising, in weight percent: f: 0 to 1 percent.
14. The ultraviolet-transmitting optical glass according to any one of claims 1 to 4, wherein SnO is not contained in the composition; and/or does not contain P2O5(ii) a And/or does not contain RO; and/or does not contain K2O; and/or no ZnO; and/or does not contain ZrO2(ii) a And/or does not contain F; and/or does not contain CeO2(ii) a And/or does not contain Ln2O3RO is one or more of MgO, CaO, SrO and BaO, Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
15. The UV-transparent optical glass according to any one of claims 1 to 4, wherein the transition temperature T of the UV-transparent optical glassg520 ℃ or lower, preferably 510 ℃ or lower, more preferably 500 ℃ or lower; and/or the linear expansion coefficient alpha of the ultraviolet-transmitting optical glass is 60 multiplied by 10-7/K～75×10-7Preferably 62X 10,/K-7/K～72×10-7More preferably 63X 10,/K-7/K～70×10-7K; and/or the stability to water of UV-transmitting optical glass DWIs 2 or more, preferably 1; and/or stability of the acid-resistance of the UV-transmitting optical glass DAIs 2 or more, preferably 1; and/or the transmittance tau of the ultraviolet-transmitting optical glass280nm0.75 or more, preferably 0.78 or more, more preferably 0.80 or more; and/or refractive index n of ultraviolet-transmitting optical glassd1.47 to 1.54, preferably 1.49 to 1.53, more preferably 1.50 to 1.525; and/or Abbe number v of ultraviolet-transmitting optical glassdIs 62 to 68, preferably 63 to 67, and more preferably 63 to 66.
16. The packaging component is characterized by being made of the ultraviolet-transmitting optical glass as claimed in any one of claims 1 to 15.
17. The glass preform is characterized by being made of the ultraviolet-transmitting optical glass according to any one of claims 1 to 15.
18. An optical element, characterized in that it is made of the ultraviolet-transmitting optical glass according to any one of claims 1 to 15 or the glass preform according to claim 17.
19. An optical device comprising the ultraviolet-transmitting optical glass according to any one of claims 1 to 15 and/or comprising the optical element according to claim 18.
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CN112794643A (en) * 2021-01-12 2021-05-14 成都光明光电股份有限公司 Optical glass, glass preform, optical element and optical instrument
CN112811812A (en) * 2021-01-12 2021-05-18 成都光明光电股份有限公司 Low-fluorescence optical glass
CN112939455A (en) * 2021-03-23 2021-06-11 成都光明光电股份有限公司 Optical glass, optical element and optical instrument
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CN112939455B (en) * 2021-03-23 2022-04-15 成都光明光电股份有限公司 Optical glass, optical element and optical instrument
CN114409253A (en) * 2022-01-24 2022-04-29 成都光明光电股份有限公司 Ultraviolet-transmitting glass
CN115784610A (en) * 2022-11-29 2023-03-14 南京华生皓光电科技有限公司 Glass tube for UVB ultraviolet fluorescent lamp for liquid crystal alignment process and application
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