Glass material

Abstract

The application provides a glass material, wherein a cation component contains, in terms of mole percentage, Si 4+ : 4-16%; B 3+ : 45-70%; La 3+ : 3-18%; Ca 2+ : 2-20%; and an anion component contains F ‑ : 1-15%; O 2‑ : 85-99%. Through reasonable component design, the glass material has high refractive index and low light absorption coefficient, and meets the application in the fields of image transmission optical fibers and the like.

Description

Technical Field

[0001] This invention relates to a glass material, and more particularly to a glass material with a low light absorption coefficient. Background Technology

[0002] Optical fibers are widely used in many aspects of people's lives. Among them, image transmission fibers are used for optical image transmission and are widely used in many fields such as industry and medicine. The key properties of image transmission fiber materials include high refractive index, low light absorption coefficient, and excellent anti-crystallization properties. The higher the refractive index of the image transmission fiber material, the more beneficial it is to increase the numerical aperture of the image transmission fiber, thereby improving the field of view and image quality. Because the optical path of image transmission fibers is relatively long, generally 1 to 5 meters, even a small amount of light absorption can cause the emitted image to appear dark or discolored, affecting the performance of the image transmission fiber. Therefore, image transmission fiber materials should have the lowest possible light absorption. On the other hand, if crystallization occurs during the glass fiber drawing process, it can lead to inherent defects in the fiber, seriously affecting the yield.

[0003] Currently, leaded glass is the most common material for image transmission fibers. Although it has advantages such as high refractive index, low light absorption coefficient, and good resistance to crystallization, the toxicity of lead necessitates its replacement. Chinese patents CN 107935381B and CN113603367B disclose lead-free high-refractive-index glass for image transmission fibers, but their glass designs contain variable-valence oxide TiO2, which often exhibits additional light absorption in the short-wavelength visible region, potentially leading to color distortion in the transmitted image. US patent US6753281 discloses an image transmission fiber glass system based on La2O3-BaO-SiO2, which, while possessing a high refractive index, exhibits a high tendency to crystallize, making it difficult to widely apply in industrial production. US patent US7087542 discloses a silicate image transmission fiber glass system with a low softening point, which has good resistance to crystallization, but contains a large amount of high-cost components such as Nb2O5 and Li2O. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a glass material with a low light absorption coefficient.

[0005] The technical solution adopted by this invention to solve the technical problem is:

[0006] (1) Glass material, expressed as molar percentage, contains the following cationic components: Si 4+ : 4-16%; B 3+ 45-70%; La 3+ 3-18%; Ca 2+ 2-20%;

[0007] The anionic component contains: F - : 1-15%; O2- 85-99%.

[0008] (2) According to the glass material described in (1), the cationic component also contains, in molar percentage: Al 3+ : 0-10%; and / or Zr 2+ : 0-3%; and / or Li + : 0-8%; and / or Na + : 0–8%; and / or K + : 0-8%; and / or Y 3+ : 0-10%; and / or Ba 2+ : 0-8%; and / or Sr 2+ 0–15%; and / or Mg 2+ 0–10%; and / or Zn 2+ 0–5%; and / or Sb 3+ : 0-1%.

[0009] (3) Glass materials, whose composition contains Si 4+ B 3+ La 3+ Ca 2+ F - and O 2- B 3+ / (La 3+ +5×Si 4+ The visible light absorption coefficient of the glass material is 0.5 to 2.0, and the average visible light absorption coefficient is 50 × 10⁻⁶. -5 / cm or less.

[0010] (4) According to the glass material described in (3), the cationic component contains, in molar percentage: Si 4+ : 4–16%; and / or B 3+ : 45-70%; and / or La 3+ +Y 3+ 7–18%; and / or Mg 2+ +Ca 2+ +Sr 2+ +Ba 2+ +Zn 2+ : 10-22%; and / or Li + +Na + +K + : 0–10%; and / or Al 3+ : 0-10%; and / or Zr 2+ 0–3%; and / or Sb 3+ 0-1%;

[0011] The anionic component contains: F - : 1-15%; and / or O2- 85-99%.

[0012] (5) The glass material according to (3) or (4) contains, in molar percentage: La 3+ : 3-18%; and / or Y 3+ : 0–10%; and / or Ca 2+ : 2-20%; and / or Li + : 0-8%; and / or Na + : 0–8%; and / or K + : 0-8%; and / or Ba 2+ : 0-8%; and / or Sr 2+ 0–15%; and / or Mg 2+ 0–10%; and / or Zn 2+ 0-5%.

[0013] (6) Glass material, expressed as a molar percentage, with the cationic component consisting of Si 4+ : 4-16%; B 3+ 45-70%; La 3 + 3-18%; Ca 2+ 2-20%; Al 3+ : 0-10%; Zr 2+ : 0-3%; Li + 0-8%; Na + 0-8%; K + : 0-8%; Y 3+ : 0-10%; Ba 2+ : 0-8%; Sr 2+ 0-15%; Mg 2+ 0-10%; Zn 2+ 0-5%; Sb 3+ Composition: 0-1%, anionic component consists of F - : 1-15%; O 2- Composition: 85-99%.

[0014] (7) The glass material according to any one of (1) to (6), expressed in molar percentage, wherein: B 3+ / (La 3+ +5×Si 4+ The value is 0.5-2.0, with B being preferred. 3+ / (La 3+ +5×Si 4+ The value is 0.55 to 1.5, with B being more preferred. 3+ / (La 3+ +5×Si 4+ The value ranges from 0.6 to 1.0.

[0015] (8) The glass material according to any one of (1) to (6), expressed as a molar percentage, wherein: 0.01 / (Si 4+ ×F - The value is 1.0 to 10.0, preferably 0.01 / (Si). 4+ ×F - The Si content is between 1.2 and 9.0, more preferably 0.01 / (Si). 4+ ×F - The value ranges from 1.6 to 7.0.

[0016] (9) The glass material according to any one of (1) to (6), expressed as a molar percentage, wherein: Ca 2+ / F - The value is 1.0–5.0, with Ca being the preferred option. 2+ / F - The value is 1.2 to 4.0, with Ca being more preferred. 2+ / F - It ranges from 1.5 to 3.25.

[0017] (10) The glass material according to any one of (1) to (6), expressed in molar percentage, wherein: La 3+ +Y 3+ 7-18%, with La being the preferred choice. 3+ +Y 3+ 8-16%, more preferably La 3+ +Y 3+ 9–14%; and / or Mg 2+ +Ca 2+ +Sr 2+ +Ba 2+ +Zn 2+ 10-22%, preferably Mg 2+ +Ca 2+ +Sr 2+ +Ba 2+ +Zn 2+ 10.5-20%, more preferably Mg 2+ +Ca 2+ +Sr 2+ +Ba 2+ +Zn 2+ : 11-18%; and / or Li + +Na + +K + 0-10%, preferably Li + +Na + +K + 0–7.5%, more preferably Li + +Na + +K + 0-5%.

[0018] (11) The glass material according to any one of (1) to (6), expressed in molar percentage, wherein: Si 4+ 5-15%, preferably Si 4+ 7-13%; and / or B 3+ 47-65%, B is preferred. 3+ : 49–62%; and / or La 3+ 4-17%, with La being the preferred choice. 3+ 6–15%; and / or Ca 2+ 3-18%, preferably Ca 2+ : 4–16%; and / or Al 3+ 0-8%, preferably Al 3+ 0–6%; and / or Zr 2+ 0-2.5%, preferably Zr 2+ : 0-2%; and / or Li + 0-3%, preferably Li + 0–2%; and / or Na + 0-3%, preferably Na + 0–2%; and / or K + 0.5-7%, K is preferred + : 1-6%; and / or Y 3+ 0-6%, preferred Y 3+ : 0-4%; and / or Ba 2+ : 0-2%; and / or Sr 2+ 0-12%, preferably Sr 2+ 2-9%; and / or Mg 2+ 0–7.5%, preferably Mg 2+ 0–5%; and / or Zn 2+ : 0-2%; and / or Sb 3+ 0-0.2%, preferably Sb 3+ : 0.01~0.1%.

[0019] (12) The glass material according to any one of (1) to (6), expressed as a molar percentage, wherein: F - 2-12%, with F being the preferred option. - 3-10%; and / or O 2- 88-98%, preferred O 2- 90-97%.

[0020] (13) According to any one of (1) to (6), Fe 3+ Content less than 50 ppm; and / or Pt 4+ Content less than 10 ppm; and / or does not contain Ba2+ ; and / or does not contain Zn 2+ ; and / or does not contain Ti 4+ ; and / or does not contain As 5+ ; and / or does not contain Pb 2+ ; and / or does not contain Tl + ; and / or does not contain Nb 5+ ; and / or does not contain Rb + ; and / or does not contain Cs + ; and / or does not contain Ta 5+ ; and / or does not contain N 3- ; and / or does not contain S 2- ; and / or does not contain SO4 2- ; and / or does not contain Cl - ; and / or does not contain Se 2- .

[0021] (14) The glass material according to any one of (1) to (6) contains Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ Two or more components, preferably containing Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ The two components in it.

[0022] (15) The refractive index of the glass material according to any one of (1) to (6) is 1.64 to 1.70, preferably 1.645 to 1.695, more preferably 1.65 to 1.69; the Abbe number is 55.0 to 61.0, preferably 55.5 to 60.5, more preferably 56.0 to 60.0.

[0023] (16) The average visible light absorption coefficient of the glass material according to any one of (1) to (6) is 50 × 10⁻⁶. -5 / cm or less, preferably 20×10 -5 / cm or less, more preferably 10×10 -5 Below / cm; and / or with an average coefficient of thermal expansion of 60×10 -7 / K~85×10 -7 / K; and / or anti-crystallization performance of D grade or above, preferably C grade or above, more preferably B grade or above; and / or acid resistance stability of Class 4 or above, preferably Class 3 or above; and / or water resistance stability of Class 2 or above, preferably Class 1; and / or clarification temperature of 1250℃ or below, preferably 1220℃ or below, more preferably 1190℃ or below.

[0024] (17) A glass preform made of any of the glass materials described in (1) to (16).

[0025] (18) A glass element made of any of the glass materials described in (1) to (16) or the glass preform described in (17).

[0026] The beneficial effects of this invention are: through reasonable component design, the glass material of this invention has a high refractive index and a low light absorption coefficient, which meets the application requirements of fields such as optical fiber for image transmission. Detailed Implementation

[0027] The embodiments of the glass material of the present invention will now be described in detail. However, the present invention is not limited to the embodiments described below, and appropriate modifications can be made to implement it within the scope of the purpose of the present invention. Furthermore, regarding repeated descriptions, although there are appropriate omissions, this will not limit the spirit of the invention. In the following text, the glass material of the present invention will sometimes be simply referred to as glass.

[0028] [Glass Materials]

[0029] The composition range of each component (ingredient) constituting the glass material of this invention is described below. In this specification, unless otherwise specified, the content of a cationic component is expressed as the molar percentage (mol%) of the cation among all cationic components, and the content of anionic components is expressed as the molar percentage (mol%) of the anion among all anionic components. The ratio between the contents of cationic components is the ratio of the molar percentage contents of each cationic component; the ratio between the contents of anionic components is the ratio of the molar percentage contents of each anionic component; and the ratio between the contents of cationic and anionic components is the ratio of the molar percentage contents of the cationic component among all cationic components to the molar percentage contents of the anionic component among all anionic components. It should be noted that when multiplication and / or division relationships are involved between components, the component content is calculated based on the actual value corresponding to its percentage content. For example, when the component content percentage is 10%, it is calculated as 0.1 in multiplication and / or division relationships.

[0030] Unless otherwise specified in the specific context, the numerical ranges listed herein include upper and lower limits. "Above" and "below" include endpoint values ​​and all integers and fractions included within the range, but are not limited to the specific values ​​listed when the range is defined. The term "and / or" is inclusive; for example, "A and / or B" means only A, or only B, or both A and B. It should be noted that the ionic valences of the components in this invention are representative values ​​used for convenience and are not distinguishable from other ionic valences. The ionic valences of the components in the glass material may exist beyond these representative values.

[0031] <About cationic components>

[0032] Si 4+ It acts as a network form in the glass of this invention and contains Si. 4+ This helps to increase the melting temperature of the glass in this invention, facilitating the production of La. 3+ Zr 4+ Melting of refractory materials such as Si. 4+ Si has the effect of improving the mechanical properties and chemical stability of glass. 4+ This also helps to reduce the light absorption coefficient of the glass in this invention. However, Si 4+ Excessive Si content will make glass formation difficult in the glass system of this invention. Therefore, in this invention... 4+ The content is 4-16%, preferably 5-15%, and more preferably 7-13%.

[0033] B 3+ B is the main network component of the glass of this invention. 3+ It can exist in the glass in the form of [BO3] or [BO4]. The glass of this invention contains B. 3+ It can make La in glass 3+ The upper limit of the content of [B] is increased, thereby enabling the glass of the present invention to achieve the desired refractive index. If B 3+ Excessive content of certain components leads to an excessively high raw material gas rate, which can cause adverse effects such as raw material splashing during the melting process. Furthermore, it results in significant volatilization during glass melting, reducing the chemical stability of the glass. Therefore, B... 3+ The content ranges from 45% to 70%, preferably from 47% to 65%, and more preferably from 49% to 62%.

[0034] Al 3+ It is a network intermediate component and has the potential to form structural units such as [AlO4], [AlO5], and [AlO6] in glass. 3+ It is beneficial to improve the chemical stability and mechanical strength of glass. Within a certain range, the presence of Al... 3+ This does not affect the performance of the glass in this invention. In this invention, Al... 3+ The content ranges from 0 to 10%, preferably from 0 to 8%, and more preferably from 0 to 6%.

[0035] Zr 4+ It is a glass network intermediate component. It contains a small amount of Zr. 4+ This is beneficial for improving the chemical stability of the glass without affecting the average light absorption coefficient of the glass of this invention. However, Zr 4+ Excessive Zr content reduces the glass's resistance to crystallization and hinders the control of its internal quality. Therefore, Zr... 4+The content is 0-3%, preferably 0-2.5%, and more preferably 0-2%.

[0036] Li + It has a significant fluxing effect in glass and reduces its high-temperature viscosity, while also helping to reduce light absorption and lower the glass transition temperature. However, the high-temperature viscosity of the glass of this invention is already low, so it is unnecessary to contain large amounts of Li, which has a low refractive index and high raw material cost. + In this invention, Li + The content is 0-8%, preferably 0-3%, and more preferably 0-2%.

[0037] Na + It belongs to the components of the glass network outer body. Na + It helps improve the melting performance of glass, relative to Li. + Na + It has advantages such as low difficulty in raw material preparation and low price. The present invention relates to Na in glass. + The content is 0-8%, preferably 0-3%, and more preferably 0-2%.

[0038] K + As a component of the network outer layer, its intrinsic absorption is extremely small, which is beneficial for reducing the light absorption coefficient of the glass. Compared to other alkali metals, Li... + Na + K + The effect of reducing the light absorption coefficient of glass is more superior. Therefore, K in the glass of this invention... + The content is 0-8%, preferably 0.5-7%, and more preferably 1-6%.

[0039] In some embodiments of the present invention, Li + Na + K + Total content of Li + +Na + +K + By controlling the concentration within the range of 0–10%, the light absorption coefficient of the glass can be reduced while preventing a deterioration in its chemical stability. Therefore, Li is preferred. + +Na + +K + The content is 0-10%, more preferably Li + +Na + +K + The content is 0-7.5%, and Li is further preferred. + +Na + +K + It ranges from 0% to 5%.

[0040] La 3+ In the glass of this invention, La mainly serves to increase the refractive index.3+ Insufficient content makes it difficult for the glass refractive index to achieve the target of this invention, resulting in a low numerical aperture and poor image transmission effect in the formed imaging fiber. However, with the development of La... 3+ The higher the content of La, the higher the light absorption coefficient of the glass. 3+ The content is 3-18%, preferably 4-17%, and more preferably 6-15%.

[0041] In some embodiments of the present invention, controlling B 3+ / (La 3+ +5×Si 4+ Within the range of 0.5 to 2.0, B can improve the glass's resistance to crystallization, optimize its coefficient of thermal expansion, and reduce its light absorption coefficient. Therefore, B is preferred. 3+ / (La 3+ +5×Si 4+ The value is 0.5 to 2.0, with B being more preferred. 3+ / (La 3+ +5×Si 4+ The value is 0.55–1.5, with B being the preferred option. 3+ / (La 3+ +5×Si 4 + The value ranges from 0.6 to 1.0.

[0042] Y 3+ Y plays a role in altering the glass network within glass. Regarding its contribution to the refractive index and hardness of glass, Y... 3+ The function and La 3+ Similarly, but its intrinsic absorption is slightly greater than that of La. 3+ And Y 3+ The price of raw materials is higher than that of La 3+ Therefore, the Y in the glass of this invention 3+ The content is 0-10%, preferably 0-6%, and more preferably 0-4%.

[0043] In some embodiments of the present invention, controlling La 3+ and Y 3+ Total content of La 3+ +Y 3+ Within the range of 7% to 18%, glass can exhibit both low visible light absorption and a high refractive index. Therefore, La is preferred. 3+ +Y 3+ The value is 7-18%, with La being more preferred. 3+ +Y 3+ The percentage is 8-16%, with further optimization of La. 3+ +Y 3+ It ranges from 9% to 14%.

[0044] Ca2+ It is a glass network intermediate component, Ca 2+ It has the effect of improving the water resistance and stability of glass. The glass contains F... - In the case of Ca 2+ It also helps improve the glass's resistance to crystallization. Therefore, Ca 2+ The content is 2-20%, preferably 3-18%, and more preferably 4-16%.

[0045] Sr 2+ It is a glass network intermediate component. Sr 2+ This is beneficial for improving the refractive index of the glass of the present invention. Within a certain range, Sr 2+ The increased content of Sr did not significantly affect the average light absorption coefficient of the glass of this invention. Therefore, Sr 2+ The content ranges from 0 to 15%, preferably from 0 to 12%, and more preferably from 2 to 9%.

[0046] Mg 2+ It is a glass network intermediate component. Compared to other divalent network intermediate components, Mg... 2+ It is most beneficial for improving the short-wave transmittance of glass, but its refractive index contribution is the lowest. Mg 2+ This is beneficial for improving the hardness of glass. In some embodiments of the present invention, without the use of Mg... 2+ Even under these conditions, the glass transmittance requirements can still be met. Therefore, Mg 2+ The content ranges from 0 to 10%, preferably from 0 to 7.5%, and more preferably from 0 to 5%.

[0047] Ba 2+ It is beneficial to increase the refractive index of glass. In the boron-lanthanum glass system, a certain content of Ba is beneficial. 2+ This is beneficial for improving the resistance to crystallization in glass. However, industrially produced Ba-containing glass... 2+ The purity of raw materials is difficult to guarantee, and the glass of this invention requires control of impurity content to ensure low light absorption in the visible light band. Therefore, Ba 2+ The content of Ba is 0-8%, preferably 0-2%, and more preferably free of Ba. 2+ .

[0048] Zn 2+ When the content is appropriate, Zn can help reduce the tendency of glass to crystallize and improve its chemical stability. However, Zn... 2+ The absorption limit of Zn is close to the visible light range, which is not conducive to achieving the high visible light transmittance of the glass of this invention. Therefore, Zn 2+ The content is 0-5%, preferably 0-2%, and more preferably Zn-free. 2+ .

[0049] Mg 2+Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ In glass, these are all intermediates in the glass network. Excessive content of these intermediates increases the proportion of non-bridging oxygen and decreases the proportion of bridging oxygen, leading to a decrease in the glass's resistance to crystallization and a reduction in short-wavelength transmittance. Therefore, in some embodiments, Mg... 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ Total Mg content 2+ +Ca 2+ +Sr 2+ +Ba 2+ +Zn 2+ Preferably 10-22%, more preferably Mg 2+ +Ca 2+ +Sr 2+ +Ba 2+ +Zn 2+ The content is 10.5%–20%, with Mg being a further preferred option. 2+ +Ca 2+ +Sr 2+ +Ba 2+ +Zn 2+ It ranges from 11% to 18%.

[0050] The different divalent network intermediate components exhibit a mixed alkaline earth metal effect, which is beneficial for improving glass chemical stability. Therefore, in some embodiments of the present invention, Mg is preferably included. 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ More than two components, preferably containing Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ The two components in it.

[0051] Sb 3+ In this invention, it can be used as a clarifying agent. 3+ Excessive Sb content reduces the ultraviolet transmittance of glass. 3+ Excessive Sb content can also reduce the short-wave visible light transmittance of the glass. However, Sb... 3+ When the content is appropriate, it is beneficial to improve the transmittance of short-wave visible light in glass. Therefore, Sb 3+ The content is 0-1%, preferably 0-0.2%, and more preferably 0.01-0.1%.

[0052] In some embodiments, to achieve the low visible light absorption effect of the glass of the present invention, in addition to meeting the above-mentioned component range, it is also necessary to control raw material impurities, standardize operations, and improve melting equipment to reduce the Fe content in the glass. 3+ Impurity content less than 50 ppm, Pt 4+ The impurity content is less than 10 ppm.

[0053] The glass of this invention preferably does not contain As, which is harmful to the environment and human body. 5+ Pb 2+ 、Tl + Components.

[0054] The glass of this invention preferably does not contain expensive Nb. 5+ 、Rb + Cs + Ta 5+ Components.

[0055] The glass of this invention preferably does not contain Ti. 4+ Components.

[0056] <About Anionic Components>

[0057] O 2- This is the main anionic component of the glass of this invention. 2- The formation of chemical bonds between the glass cationic component and the glass of this invention is beneficial to the composition of the glass of this invention. If O 2- If the content is too low, the glass's resistance to crystallization is difficult to guarantee. However, if O 2- Excessive content, especially in O 2- If the absorption coefficient is 100%, it is difficult to meet the requirement of low light absorption coefficient for the glass of this invention. Therefore, O 2- The content ranges from 85% to 99%, preferably from 88% to 98%, and more preferably from 90% to 97%.

[0058] F - It is an essential anionic component of the glass of this invention. In the glass system of this invention, F - Before the content exceeds a certain range, it does not affect the anti-crystallization properties of the glass of this invention. - It can significantly reduce the light absorption coefficient of glass in the 500–800 nm wavelength range. In F - When the content exceeds a certain range, it significantly reduces the light absorption coefficient of glass in the 400–500 nm wavelength range. With F - As the content increases, the refractive index of the glass gradually decreases. - When the content exceeds a certain range, the chemical stability and anti-crystallization properties of the glass do not meet the requirements of the glass of this invention. Therefore, F -The content ranges from 1% to 15%, preferably from 2% to 12%, and more preferably from 3% to 10%.

[0059] Si is present in large quantities in the molten glass. 4+ and F - In this case, because the saturated vapor pressure of SiF4 is significantly higher than that of other fluorides, it will lead to an increase in the amount of fluorine (F) in the glass. - Increased evaporation is detrimental to the consistency control of glass products. On the other hand, F - Increasing the SiO2 content increases the melting rate of raw materials other than SiO2 in the glass, resulting in insufficient time for solid-state reactions between SiO2 and other fusible materials. This leads to SiO2 becoming difficult to melt in the glass melt, forming SiO2-dominated stones within the glass, potentially causing internal defects and reducing the glass's light transmittance. In some embodiments of the present invention, by controlling 0.01 / (SiO2... 4+ ×F - Within the range of 1.0 to 10.0, it can significantly inhibit F. - This reduces the volatility of the glass, improves product consistency and production adaptability, and lowers the light absorption coefficient. Therefore, a value of 0.01 / (Si) is preferred. 4+ ×F - The value is 1.0 to 10.0, more preferably 0.01 / (Si). 4+ ×F - The Si content is 1.2 to 9.0, with a further preferred value of 0.01 / (Si). 4+ ×F - The value ranges from 1.6 to 7.0.

[0060] In some embodiments of the present invention, controlling Ca 2+ / F - Within the range of 1.0 to 5.0, Ca is beneficial for improving the glass's resistance to crystallization and chemical stability, and optimizing its coefficient of thermal expansion. Therefore, Ca is preferred. 2+ / F - The value is 1.0 to 5.0, with Ca being more preferred. 2+ / F - The value of Ca is 1.2–4.0, with further optimization. 2+ / F - It ranges from 1.5 to 3.25.

[0061] The glass of this invention is preferably free of nitrogen (N). 3- S 2- SO4 2- Cl - Se 2- Anionic components are present. However, the possibility that these anionic components may exist as impurities cannot be ruled out.

[0062] The terms "not containing" and "0%" as used herein mean that the component was not intentionally added to the glass of this invention as a raw material; however, as raw materials and / or equipment for producing glass, there may be certain impurities or components that are not intentionally added, which may be present in small or trace amounts in the final glass, and such situations are also within the scope of protection of this patent.

[0063] The properties of the glass material of the present invention will now be described.

[0064] <Refractive Index and Abbe Number>

[0065] The refractive index (n) of glass d ) and Abbe number (ν d Test according to the method specified in GB / T 7962.1—2010.

[0066] In some embodiments, the refractive index (n) of the glass of the present invention d The lower limit of the refractive index (n) is 1.64, preferably 1.645, and more preferably 1.65; in some embodiments, the refractive index (n) of the glass of the present invention is... d The upper limit of ) is 1.70, the preferred upper limit is 1.695, and the more preferred upper limit is 1.69.

[0067] In some embodiments, the Abbe number (ν) of the glass of the present invention d The lower limit of the Abbe number (ν) is 55.0, preferably 55.5, and more preferably 56.0; in some embodiments, the Abbe number (ν) of the glass of the present invention is... d The upper limit of ) is 61.0, the preferred upper limit is 60.5, and the more preferred upper limit is 60.0.

[0068] <Average absorption coefficient of visible light>

[0069] The internal transmittance of glass was tested according to the method specified in GB / T 7962.9—2010. Specifically, the glass sample was processed into two large, polished samples with thicknesses of 5 mm and 15 mm respectively, and the visible light transmittance was measured using a UV-Vis spectrophotometer. The transmittance of the 5 mm thick sample was defined as T5, and the transmittance of the 15 mm thick sample was defined as T... 15 The internal transmittance T of a 10mm glass is:

[0070]

[0071] Based on the internal transmittance of the glass, the average visible light absorption coefficient (α) of the glass of this invention is... 平均 It can be calculated using the following formula:

[0072]

[0073] That is, the light absorption coefficient corresponding to the internal transmittance values ​​of a 10mm thick glass sample within the range of 400–800nm ​​is averaged. When using the above formula, the wavelengths corresponding to the internal transmittance values ​​between 400 and 800nm ​​should be uniformly selected, meaning the difference between any two adjacent wavelength values ​​is equal, and the interval between two adjacent wavelength values ​​should be less than or equal to 20nm. When using the above formula, the wavelengths corresponding to the internal transmittance values ​​must include 400nm and 800nm.

[0074] In some embodiments, the average visible light absorption coefficient (α) of the glass of the present invention is... 平均 ) is 50×10 -5 / cm or less, preferably 20×10 -5 / cm or less, more preferably 10×10 -5 / cm or less.

[0075] <Average thermal expansion coefficient>

[0076] The average coefficient of thermal expansion of glass was tested according to the method specified in GB / T 7962.16—2010.

[0077] The average thermal expansion coefficient mentioned in this invention refers to the average thermal expansion coefficient in the range of 20 to 120°C.

[0078] In some embodiments, the average coefficient of thermal expansion of the glass of the present invention is 60 × 10⁻⁶. -7 / K~85×10 -7 / K.

[0079] Anti-crystallization properties

[0080] The anti-crystallization properties of the glass of this invention are defined according to the following method.

[0081] The glass was cut into multiple 20×20×20mm cubes, and the surfaces were cleaned with deionized water. The cubes were then placed in muffle furnaces at 700℃, 725℃, and 750℃ respectively. After holding at these temperatures for a certain time, the samples were removed and cooled to room temperature at a rate of 20–100℃ / h. The presence of crystalline particles inside the samples was then observed. The crystallization performance of the glass was defined as AF grade according to the standards shown in Table 1.

[0082] Table 1.

[0083]

[0084] For the glass material of this invention, a crystallization resistance of grade D can be considered as having feasible production adaptability and usable secondary hot working properties; a crystallization resistance of grade C can be considered as having good secondary hot working adaptability.

[0085] In some embodiments, the anti-crystallization performance of the glass of the present invention is grade D or above, preferably grade C or above, and more preferably grade B or above.

[0086] <Stability under water resistance>

[0087] Water resistance stability of glass (D) W Test according to the method specified in GB / T17129.

[0088] In some embodiments, the water resistance stability (D) of the glass of the present invention is... W There are two or more categories, with category 1 being preferred.

[0089] <Stability under acid conditions>

[0090] Glass acid resistance stability (D) A Test according to the method specified in GB / T17129.

[0091] In some embodiments, the acid resistance stability (D) of the glass of the present invention is... A It should be of 4 or more categories, preferably 3 or more categories.

[0092] [Glass Manufacturing Methods]

[0093] The glass of the present invention can be prepared using a known single-crucible glass melting process or a continuous glass melting process.

[0094] The manufacturing method of the glass of this invention is as follows: The glass of this invention is produced using conventional raw materials and conventional processes. It uses composite salts (carbonates, nitrates, sulfates, etc.), hydroxides, oxides, fluorides, etc., as raw materials. After being batched according to conventional methods, the batched charge is added to a melting furnace at 900–1250°C for melting. After clarification, stirring, and homogenization, a homogeneous molten glass without visible bubbles and unmelted substances is obtained. This molten glass is then cast in a mold and annealed. Those skilled in the art can appropriately select raw materials, process methods, and process parameters according to actual needs.

[0095] The glass of this invention has the advantage of a low refining temperature. This advantage helps reduce the corrosion of the melting vessel by the molten glass, reduces volatilization, and helps reduce the impurity content in the glass, thereby reducing the visible light absorption of the glass. The glass contains F... - In this case, lowering the glass refining temperature also has the effect of reducing F - Advantages of low volatile matter content. The refining temperature of the glass of this invention is preferably below 1250°C, more preferably below 1220°C, and even more preferably below 1190°C. The refining temperature mentioned in this invention refers to the highest temperature experienced during various time periods of the glass melting process.

[0096] [Glass prefabrication and glass components]

[0097] The glass of this invention can be made into any usable lens, prism, blank, optical fiber preform, optical fiber, or other glass preform or glass element by cold processing methods including grinding, cutting, slicing, polishing, and / or hot processing methods including heating molding, extrusion, drawing, blowing, etc.

[0098] [Example]

[0099] To further clarify and illustrate the technical solution of the present invention, the following non-limiting embodiments are provided in Tables 2 to 4. Furthermore, the properties of each glass were measured using the test method described in the present invention, and the measurement results are shown in Tables 2 to 4.

[0100] Table 2.

[0101]

[0102]

[0103] Table 3.

[0104]

[0105]

[0106] Table 4.

[0107]

[0108]

Claims

1. A glass material, characterized in that, The cationic component contains, in molar percentage: Si 4+ : 4~16%; B 3+ : 45~70%; La 3+ 3-18%; Ca 2+ : 2~20%; La 3+ +Y 3+ 7-18%; The anionic component contains: F - : 1~15%; O 2- 85-99%, Ca 2+ / F - The refractive index of the glass material is 1.0 to 5.0, and the Abbe number is 1.64 to 1.70, with an Abbe number of 55.0 to 61.

0.

2. The glass material according to claim 1, characterized in that, The cationic component also contains, in molar percentage: Al 3+ : 0–10%; and / or Zr 2+ : 0–3%; and / or Li + : 0–8%; and / or Na + : 0–8%; and / or K + : 0–8%; and / or Y 3+ : 0–10%; and / or Ba 2+ : 0–8%; and / or Sr 2+ : 0–15%; and / or Mg 2+ : 0–10%; and / or Zn 2+ : 0–5%; and / or Sb 3+ : 0~1%.

3. A glass material, characterized in that, The cationic component contains, in molar percentage: Si 4+ : 4~16%; B 3+ : 45~70%; La 3+ 3-18%; Ca 2+ : 2-20%; the anionic component contains: F - : 1~15%; O 2- 85-99%, of which B 3+ / (La 3+ +5×Si 4+ The value of Ca is 0.5–2.

0. 2+ / F - The value ranges from 1.0 to 5.0, La. 3+ +Y 3+ The visible light absorption coefficient of the glass material is 7-18%, and the average visible light absorption coefficient is 50 × 10⁻⁶. -5 The refractive index is below 1.64 to 1.70 and the Abbe number is 55.0 to 61.

0.

4. The glass material according to claim 3, characterized in that, The cationic component contains, in molar percentage: Mg 2+ +Ca 2+ +Sr 2+ +Ba 2+ +Zn 2+ : 10–22%; and / or Li + +Na + +K + : 0–10%; and / or Al 3+ : 0–10%; and / or Zr 2+ : 0–3%; and / or Sb 3+ : 0~1%.

5. The glass material according to claim 3, characterized in that, Expressed as a mole percentage, it contains: Y 3+ : 0–10%; and / or Li + : 0–8%; and / or Na + : 0–8%; and / or K + : 0–8%; and / or Ba 2+ : 0–8%; and / or Sr 2+ : 0–15%; and / or Mg 2+ : 0–10%; and / or Zn 2+ : 0-5%.

6. A glass material, characterized in that, The cationic component, expressed as a molar percentage, consists of Si 4+ : 4~16%; B 3+ : 45~70%; La 3+ 3-18%; Ca 2+ : 2~20%; Al 3+ : 0~10%; Zr 2+ : 0~3%; Li + : 0~8%; Na + : 0~8%; K + : 0~8%; Y 3+ : 0~10%; Ba 2+ : 0~8%; Sr 2+ 0-15%; Mg 2+ : 0~10%; Zn 2+ : 0~5%; Sb 3+ Composition: 0-1%, anionic component consists of F - : 1~15%; O 2- Composed of 85-99% Ca 2+ / F - The value ranges from 1.0 to 5.0, La. 3+ +Y 3+ The refractive index of the glass material is 7-18%, the refractive index is 1.64-1.70, and the Abbe number is 55.0-61.

0.

7. The glass material according to any one of claims 1 to 2, 6, characterized in that, Expressed as a mole percentage, where: B 3 + / (La 3+ +5×Si 4+ The value ranges from 0.5 to 2.

0.

8. The glass material according to any one of claims 1 to 6, characterized in that, Expressed as a mole percentage, where: B 3+ / (La 3+ +5×Si 4+ The value ranges from 0.55 to 1.

5.

9. The glass material according to any one of claims 1 to 6, characterized in that, Expressed as a mole percentage, where: B 3+ / (La 3+ +5×Si 4+ The value ranges from 0.6 to 1.

0.

10. The glass material according to any one of claims 1 to 6, characterized in that, Expressed as a mole percentage, where: 0.01 / (Si) 4+ ×F - The value ranges from 1.0 to 10.

0.

11. The glass material according to any one of claims 1 to 6, characterized in that, Expressed as a mole percentage, where: 0.01 / (Si) 4+ ×F - () in the range of 1.2 to 9.

0.

12. The glass material according to any one of claims 1 to 6, characterized in that, Expressed as a mole percentage, where: 0.01 / (Si) 4+ ×F - The value ranges from 1.6 to 7.

0.

13. The glass material according to any one of claims 1 to 6, characterized in that, Expressed as a mole percentage, where: Ca 2 + / F - The value ranges from 1.2 to 4.

0.

14. The glass material according to any one of claims 1 to 6, characterized in that, Expressed as a mole percentage, where: Ca 2 + / F - It ranges from 1.5 to 3.

25.

15. The glass material according to any one of claims 1 to 3, 5 to 6, characterized in that, Expressed as a mole percentage, where: Mg 2+ +Ca 2+ +Sr 2+ +Ba 2+ +Zn 2+ : 10–22%; and / or Li + +Na + +K + : 0~10%.

16. The glass material according to any one of claims 1 to 6, characterized in that, Expressed as a mole percentage, where: La 3 + +Y 3+ : 8–16%; and / or Mg 2+ +Ca 2+ +Sr 2+ +Ba 2+ +Zn 2+ : 10.5–20%; and / or Li + +Na + +K + : 0~7.5%.

17. The glass material according to any one of claims 1 to 6, characterized in that, Expressed as a mole percentage, where: La 3 + +Y 3+ : 9–14%; and / or Mg 2+ +Ca 2+ +Sr 2+ +Ba 2+ +Zn 2+ : 11-18%; and / or Li + +Na + +K + : 0-5%.

18. The glass material according to any one of claims 1 to 6, characterized in that, Expressed as a mole percentage, where: Si 4 + : 5-15%; and / or B 3+ : 47–65%; and / or La 3+ : 4–17%; and / or Ca 2+ 3–18%; and / or Al 3+ : 0–8%; and / or Zr 2+ : 0–2.5%; and / or Li + : 0–3%; and / or Na + : 0–3%; and / or K + : 0.5–7%; and / or Y 3+ : 0–6%; and / or Ba 2+ : 0–2%; and / or Sr 2+ : 0–12%; and / or Mg 2+ : 0–7.5%; and / or Zn 2+ : 0–2%; and / or Sb 3+ : 0~0.2%.

19. The glass material according to any one of claims 1 to 6, characterized in that, Expressed as a mole percentage, where: Si 4 + 7-13%; and / or B 3+ : 49–62%; and / or La 3+ : 6–15%; and / or Ca 2+ : 4–16%; and / or Al 3+ : 0–6%; and / or Zr 2+ : 0–2%; and / or Li + : 0–2%; and / or Na + : 0–2%; and / or K + : 1-6%; and / or Y 3+ : 0–4%; and / or Sr 2 + 2-9%; and / or Mg 2+ : 0–5%; and / or Sb 3+ : 0.01~0.1%.

20. The glass material according to any one of claims 1 to 6, characterized in that, Expressed as a mole percentage, where: F - : 2-12%; and / or O 2- 88-98%.

21. The glass material according to any one of claims 1 to 6, characterized in that, Expressed as a mole percentage, where: F - : 3-10%; and / or O 2- : 90-97%.

22. The glass material according to any one of claims 1 to 6, characterized in that, Fe 3+ Content less than 50 ppm; and / or Pt 4+ Content less than 10 ppm; and / or does not contain Ba 2+ ; and / or does not contain Zn 2+ ; and / or does not contain Ti 4+ ; and / or does not contain As 5 + ; and / or does not contain Pb 2+ ; and / or does not contain Tl + ; and / or does not contain Nb 5+ ; and / or does not contain Rb + ; and / or does not contain Cs + ; and / or does not contain Ta 5+ ; and / or does not contain N 3- ; and / or does not contain S 2- ; and / or does not contain SO4 2- ; and / or does not contain Cl - ; and / or does not contain Se 2- .

23. The glass material according to any one of claims 1 to 6, characterized in that, Contains Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ Two or more components in it.

24. The glass material according to any one of claims 1 to 6, characterized in that, Contains Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ The two components in it.

25. The glass material according to any one of claims 1 to 6, characterized in that, The glass material has a refractive index of 1.645 to 1.695 and an Abbe number of 55.5 to 60.

5.

26. The glass material according to any one of claims 1 to 6, characterized in that, The glass material has a refractive index of 1.65 to 1.69 and an Abbe number of 56.0 to 60.

0.

27. The glass material according to any one of claims 1 to 2, 6, characterized in that, The average visible light absorption coefficient of the glass material is 50 × 10⁻⁶. -5 / cm or less.

28. The glass material according to any one of claims 1 to 6, characterized in that, The average visible light absorption coefficient of the glass material is 20 × 10⁻⁶. -5 Below / cm; and / or with an average coefficient of thermal expansion of 60×10 -7 / K~85×10 -7 / K; and / or anti-crystallization performance of D grade or above; and / or acid resistance stability of Class 4 or above; and / or water resistance stability of Class 2 or above; and / or clarification temperature below 1250℃.

29. The glass material according to any one of claims 1 to 6, characterized in that, The average visible light absorption coefficient of the glass material is 10 × 10⁻⁶. -5 / cm or less; and / or anti-crystallization performance of grade C or above; and / or acid resistance stability of class 3 or above; and / or water resistance stability of class 1; and / or clarification temperature of 1220℃ or less.

30. The glass material according to any one of claims 1 to 6, characterized in that, The glass material has an anti-crystallization performance of grade B or above; and / or a clarification temperature of 1190°C or below.

31. A glass precast component, characterized in that, It is made of the glass material described in any one of claims 1 to 30.

32. A glass element, characterized in that, It is made using any one of the glass materials described in claims 1 to 30 or the glass preform described in claim 31.

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