Patent Application
20240343634
The present invention relates to an optical glass, in particular to an optical glass with a refractive index of 1.89-1.96 and an Abbe number of 20-28.
The glass with refractive index of 1.89-1.96 and Abbe number of 20-28 belongs to flint glass with high refractive index. Such glass has higher refractive index and dispersion. When such glass is coupled with coronal glass, chromatic aberration and secondary spectrum can be effectively eliminated. At the same time, total optical length of lens can be effectively shortened to miniaturize the imaging system. Therefore, this type of glass has a broad application prospect in optical design.
In the prior art, the flint glass with high refractive index usually adopts P2O5—Nb2O5—TiO2—RO glass system (i.e., phosphate system), such as an optical glass with refractive index of 1.80-1.95 and Abbe number of 19-28 disclosed in CN200710088277.4. Compared with silicate (borate) glass system, phosphate system glass has the following problems: 1) the production of the phosphate system glass is more difficult than that of silicate (borate) glass, and the production cost is higher; 2) the raw material cost of the phosphate system glass is higher than that of the silicate (borate) glass; 3) the phosphate glass is higher than the silicate (borate) glass in terms of platinum vessel corrosion (consumption) used in the production process, and meanwhile the platinum vessel that has been used for producing phosphate glass requires special purification treatment during recycling, thereby further increasing the production cost; 4) phosphate glass has greater environmental load during production. Based on the reasons above, how to obtain flint glass with refractive index of 1.89-1.96 and Abbe number of 20-28 in the silicate (borate) glass system has become a new topic in optical glass research.
A technical problem to be solved by the present invention is to provide a flint optical glass with a refractive index of 1.89-1.96 and an Abbe number of 20-28.
To solve the technical problem, the technical scheme of the present invention provides:
An optical glass, wherein components thereof are represented by weight percentage, comprising: 12-30% of SiO2; 6-20% of Nb2O5; 15-35% of TiO2; 15-35% of BaO; 1-10% of ZrO2.
Furthermore, the optical glass, wherein components thereof are represented by weight percentage, further comprising: 0-6% of B2O3; and/or 0-10% of WO3; and/or 0-8% of ZnO; and/or 0-3% of Li2O; and/or 0-8% of Na2O; and/or 0-5% of K2O; and/or 0-8% of SrO; and/or 0-12% of CaO; and/or 0-8% of MgO; and/or 0-10% of Ln2O3; and/or 0-5% of Al2O3; and/or 0-1% of clarifying agent, the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3, and the clarifying agent is one or more of Sb2O3, SnO2, SnO, and CeO2.
An optical glass, wherein components thereof are represented by weight percentage, consisting of: 12-30% of SiO2; 6-20% of Nb2O5; 15-35% of TiO2, 15-35% of BaO; 1-10% of ZrO2; 0-6% of B2O3; 0-10% of WO3; 0-8% of ZnO; 0-3% of Li2O; and 0-8% of Na2O; 0-5% of K2O; 0-8% of SrO; 0-12% of CaO; 0-8% of MgO; 0-10% of Ln2O3; 0-5% of Al2O3; 0-1% of clarifying agent, the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3, and the clarifying agent is one or more of Sb2O3, SnO2, SnO, and CeO2.
Furthermore, the optical glass, wherein components thereof are represented by weight percentage, in which: Nb2O5/BaO is 0.2-1.2, Nb2O5/BaO is preferably 0.2-1.0, Nb2O5/BaO is more preferably 0.25-0.9, and Nb2O5/BaO is further preferably 0.3-0.8.
Furthermore, the optical glass, wherein components thereof are represented by weight percentage, in which: TiO2/(Nb2O5+ZrO2) is 0.6-5.5, TiO2/(Nb2O5+ZrO2) is preferably 0.7-4.0, TiO2/(Nb2O5+ZrO2) is more preferably 0.8-3.0, and TiO2/(Nb2O5+ZrO2) is further preferably 1.0-2.5.
Furthermore, the optical glass, wherein components thereof are represented by weight percentage, in which: SiO2/(Nb2O5+TiO2) is 0.3-1.3, SiO2/(Nb2O5+TiO2) is preferably 0.35-1.0, and SiO2/(Nb2O5+TiO2) is more preferably 0.4-0.8.
Furthermore, the optical glass, wherein components thereof are represented by weight percentage, in which: B2O3/SiO2 is below 0.4, B2O3/SiO2 is preferably 0.01-0.3, and B2O3/SiO2 is more preferably 0.03-0.2.
Furthermore, the optical glass, wherein components thereof are represented by weight percentage, in which: Na2O/CaO is below 5.0, Na2O/CaO is preferably 0.01-3.0, and Na2O/CaO is more preferably 0.05-2.5.
Furthermore, the optical glass, wherein components thereof are represented by weight percentage, in which: (ZnO+SrO+Ln2O3)/SiO2 is below 0.7, (ZnO+SrO+Ln2O3)/SiO2 is preferably below 0.6, (ZnO+SrO+Ln2O3)/SiO2 is more preferably below 0.5, and (ZnO+SrO+Ln2O3)/SiO2 is further preferably below 0.3.
Furthermore, the optical glass, wherein components thereof are represented by weight percentage, in which: Li2O/B2O3 is below 0.5, Li2O/B2O3 is preferably below 0.3, Li2O/B2O3 is more preferably below 0.1, and Li2O/B2O3 is further preferably below 0.05.
Furthermore, the optical glass, wherein components thereof are represented by weight percentage, in which: (SiO2+TiO2)/(Nb2O5+ZrO2+CaO+BaO) is 0.5-2.2, (SiO2+TiO2)/(Nb2O5+ZrO2+CaO+BaO) is preferably 0.6-2.0, (SiO2+TiO2)/(Nb2O5+ZrO2+CaO+BaO) is more preferably 0.8-1.8, and (SiO2+TiO2)/(Nb2O5+ZrO2+CaO+BaO) is further preferably 0.9-1.5.
Furthermore, the optical glass, wherein components thereof are represented by weight percentage, in which: 10×Li2O/Nb2O5 is below 0.7, 10×Li2O/Nb2O5 is preferably below 0.4, and 10×Li2O/Nb2O5 is more preferably below 0.2.
Furthermore, the optical glass, wherein components thereof are represented by weight percentage, in which: SiO2 is 15-25%, SiO2 is preferably 16-23%; and/or Nb2O5 is 7-18%, Nb2O5 is preferably 8-17%; and/or TiO2 is 18-32%, TiO2 is preferably 20-30%; and/or BaO is 18-32%, BaO is preferably 20-30%; and/or ZrO2 is 2-8%, ZrO2 is preferably 2-7%; and/or B2O3 is 0.1-5%, B2O3 is preferably 0.5-4%; and/or WO3 is 0-5%, WO3 is preferably 0-2%; and/or ZnO is 0-5%, ZnO is preferably 0-2%; and/or Li2O is 0-2%, Li2O is preferably 0-1%; and/or Na2O is 0-6%, Na2O is preferably 0.5-5%; and/or K2O is 0-3%, K2O is preferably 0-2%; and/or SrO is 0-4%, SrO is preferably 0-2%; and/or CaO is 1-9%, CaO is preferably 3-7%; and/or MgO is 0-4%, MgO is preferably 0-2%; and/or Ln2O3 is 0-9%, Ln2O3 is preferably 0-7%; and/or Al2O3 is 0-3%, Al2O3 is preferably 0-2%; and/or clarifying agent is 0-0.5%, clarifying agent is preferably 0-0.2%, the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3, and the clarifying agent is one or more of Sb2O3, SnO2, SnO, and CeO2.
Furthermore, the optical glass does not contain ZnO; and/or does not contain Li2O; and/or does not contain P2O5; and/or does not contain Bi2O3; and/or does not contain Ta2O5; and/or does not contain TeO2, and/or does not contain WO3.
Furthermore, refractive index nd of the optical glass is 1.89-1.96, preferably 1.90-1.95, more preferably 1.91-1.94; and Abbe number vd is 20-28, preferably 21-27, more preferably 22-26.
Furthermore, λ70 of the optical glass is below 460 nm, λ70 is preferably below 450 nm, λ70 is more preferably below 440 nm; and/or λ5 is below 400 nm, λ5 is preferably below 390 nm, as is more preferably below 380 nm; and/or acid resistance stability DA is above Class 2, preferably Class 1; and/or water resistance stability DW is above Class 2, preferably Class 1; and/or upper limit of devitrification temperature is below 1200° C., preferably below 1160° C., more preferably below 1150° C., further preferably below 1140° C.; and/or Young's modulus E is above 9000×107/Pa, preferably above 9500×107/Pa, more preferably above 10000×107/Pa, further preferably above 10500×107/Pa; and/or thermal expansion coefficient α100-300° C. is below 110×10−7/K, preferably below 105×10−7/K, more preferably below 100×10−7/K; density ρ is below 4.30 g/cm3, preferably below 4.20 g/cm3, more preferably below 4.10 g/cm3; and/or abrasion degree FA is above 150, preferably above 180, more preferably 200-300; and/or relative partial dispersion Pg,F is 0.6000-0.6500, preferably 0.6100-0.6400, more preferably 0.6150-0.6250.
A glass preform is made of the above-mentioned optical glass.
An optical element, made of the above-mentioned optical glass or made of the above-mentioned glass preform.
An optical instrument, comprising the above-mentioned optical glass, or comprising the above-mentioned optical element.
The beneficial effects of the present invention are as follows: through rational component proportion, the optical glass of the present invention obtains the optical glass with a refractive index of 1.89-1.96 and an Abbe number of 20-28 in silicate (borate) system; the cost for raw material and production of this optical glass is lower, and the environmental load is smaller.
The implementations of the optical glass provided by the present invention will be described in detail below, but the present invention is not limited to the following implementations. Appropriate changes may be made within the scope of the purpose of the present invention for implementation. In addition, the repeated descriptions will not limit the aim of the present invention although with appropriate omissions. The optical glass provided by the present invention is sometimes referred to as glass in the following content.
Hereinafter, the components of the optical glass provided by the present invention will be described. If not specified herein, the content of each component is expressed in weight percentage (wt %) relative to the total glass materials converted into oxide composition. “Converted into oxide composition” therein refers to that the total weight of this oxide is taken as 100% when the oxide, compound salt and hydroxide, used as raw materials for the composition of the optical glass of the present invention, are decomposed and transformed into oxides during melting.
Unless otherwise noted in specific circumstances, the numerical range listed herein includes upper and lower limits, and the words “above” and “below” include the endpoint values as well as all integers and fractions within the range, but not limited to the specific values listed when the range is limited. The term “about” as used herein refers to that formulations, parameters and other quantities as well as characteristics are not, and do not need to be, accurate, and may be approximate and/or greater or lower if necessary, reflecting tolerances, conversion factors, measurement errors, etc. “And/or” mentioned herein is inclusive. For example, “A and/or B” refers to only A, or only B, or both A and B.
SiO2, as a network forming body of the glass provided by the present invention, features having the viscosity that maintains chemical stability and is suitable for the molding of molten glass, increasing the devitrification resistance of the glass, and decreasing the erosion of molten glass liquid to refractory materials. If the content of SiO2 is lower than 12%, it is difficult to achieve the above-mentioned effect. Therefore, the lower limit of the content of SiO2 is 12%, preferably 15%, more preferably 16%. If the content of SiO2 is higher than 30%, the melting performance of the glass will decrease, and the transition temperature will rise. Therefore, the upper limit of the content of SiO2 is 30%, preferably 25%; more preferably 23%. In some implementations, it can comprise about 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5% or 30% of SiO2.
B2O3 can improve the thermal stability of the glass, increase the melting performance of the glass, inhibit the rapid escape of gas when the raw material is melted in order to avoid “cylinder” problem. An appropriate amount of B2O3 can enable it to be easier to obtain the glass without molten residue of glass raw material. However, when the content of B2O3 is excessive, the refractive index of the glass decreases and the thermal stability becomes poor. Therefore, the content of B2O3 in the present invention is below 6%, preferably 0.1-5%, more preferably 0.5-4%. In some implementations, it can comprise about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, or 6% of B2O3.
In some implementations of the present invention, the ratio of the content of B2O3 to the content of SiO2, i.e., B2O3/SiO2, is controlled to be below 0.4, which is conducive to improving the chemical stability of the glass. Therefore, B2O3/SiO2 is preferably below 0.4. Furthermore, it is also conducive to optimizing the Young's modulus and abrasiveness of the glass by making B2O3/SiO2 within a range of 0.01-0.3. Therefore, B2O3/SiO2 is more preferably 0.01-0.3, and B2O3/SiO2 is further preferably 0.03-0.2. In some implementations, the value of B2O3/SiO2 can be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4.
Nb2O5, a high-refraction high-dispersion component, can increase the refractive index and devitrification resistance of the glass, and decrease the thermal expansion coefficient of the glass. The present invention obtains the above-mentioned effect by comprising over 6% of Nb2O5. The content of Nb2O5 is preferably over 7%, more preferably over 8%. If the content of Nb2O5 exceeds 20%, the thermal stability and chemical stability of the glass will be decreased and the light transmittance will be reduced. Therefore, the upper limit of the content of Nb2O5 in the present invention is 20%, preferably 18%, more preferably 17%. In some implementations, it can comprise about 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5% or 20% of Nb2O5.
TiO2 can increase the refractive index and dispersion of the glass and can be involved in the formation of glass network. An appropriate amount of TiO2 can make the glass more stable and decrease the high-temperature viscosity of the glass. The present invention obtains the above-mentioned effect by comprising above 15% of TiO2, preferably comprising above 18% of TiO2, more preferably comprising above 20% of TiO2. If the content of TiO2 exceeds 35%, devitrification of the glass will tend to increase and the transition temperature will rise, and meanwhile the glass will become easy to stain during press molding. Therefore, the content of TiO2 in the present invention is below 35%, the content of TiO2 is preferably below 32%, more preferably below 30%. In some implementations of the present invention, it can comprise about 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5% or 35% of TiO2.
In some implementations of the present invention, by controlling the ratio of the content of SiO2 to the total content of Nb2O5 and TiO2 (Nb2O5+TiO2), i.e., SiO2/(Nb2O5+TiO2) within a range of 0.3-1.3, it is beneficial for the glass to obtain the appropriate abrasiveness and relative partial dispersion while decreasing the thermal expansion coefficient and density of the glass. Therefore, SiO2/(Nb2O5+TiO2) is preferably 0.3-1.3, SiO2/(Nb2O5+TiO2) is more preferably 0.35-1.0, and SiO2/(Nb2O5+TiO2) is further preferably 0.4-0.8. In some implementations of the present invention, the value of SiO2/(Nb2O5+TiO2) can be 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25 or 1.3.
WO3 can enhance the refractive index and dispersion of the glass, but the effect is not as good as Nb2O5 and TiO2, and it does not enjoy a cost advantage. Meanwhile, it will also lead to a decrease in light transmittance of the glass. Therefore, the content of WO3 in the present invention is 0-10%, preferably 0-5%, more preferably 0-2%, further preferably 0%, In some implementations, it can comprise about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10% of WO3.
ZnO can adjust the refractive index and dispersion of the glass, and decrease the transition temperature of the glass. However, if the content of ZnO exceeds 8%, devitrification resistance of the glass will be reduced, and meanwhile the high-temperature viscosity will be small to bring difficulties to the molding, and increase the thermal expansion coefficient and refractive index temperature coefficient of the glass. Therefore, the content of ZnO in the present invention is 0-8%, preferably 0-5%, more preferably 0-2%. In some implementations, it further preferably contains no ZnO. In some implementations, it can comprise about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or 8% of ZnO.
Li2O can decrease the transition temperature of the glass and improve the melting performance of the glass. However, if the content of Li2O is high, it will not be conducive to the chemical stability, devitrification resistance capability and thermal expansion coefficient of the glass. Therefore, the content of Li2O in the present invention is below 3%, preferably below 2%, more preferably below 1%. In some implementations, it further preferably contains no Li2O. In some implementations, it can comprise about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9% or 3% of Li2O.
In some implementations of the present invention, by making the ratio of the content of Li2O to the content of B2O3, i.e., Li2O/B2O3, to be below 0.5, it can increase the chemical stability of the glass and the resistance to surface devitrification of secondary compression, and optimize the abrasiveness of the glass. Therefore, Li2O/B2O3 is preferably below 0.5, Li2O/B2O3 is more preferably below 0.3, Li2O/B2O3 is further preferably below 0.1, and Li2O/B2O3 is more further preferably below 0.05. In some implementations, the value of Li2O/B2O3 can be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49 or 0.5.
In some implementations of the present invention, by making 10×Li2O/Nb2O5 to be below 0.7, it is conductive to increasing the chemical stability of the glass and the resistance to devitrification of secondary compression, and increasing the Young's modulus of the glass. Therefore, 10×Li2O/Nb2O5 is preferably below 0.7, 10×Li2O/Nb2O5 is more preferably below 0.4, and 10×Li2O/Nb2O5 is further preferably below 0.2. In some implementations of the present invention, the value of 10×Li2O/Nb2O5 can be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.5, 0.55, 0.6, 0.65 or 0.7.
Na2O can improve the melting performance of the glass and increase the melting effect of the glass, and meanwhile can decrease the transition temperature of the glass. In the present invention, an appropriate amount of Na2O can also improve the light transmittance of the glass. If the content of Na2O exceeds 8%, the chemical stability and weather resistance of the glass will be decreased. Therefore, the content of Na2O is 0-8%, the content of Na2O is preferably 0-6%, and the content of Na2O is more preferably 0.5-5%. In some implementations, it can comprise about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or 8% of Na2O.
K2O can improve the thermal stability and melting performance of the glass. However, if the content of K2O exceeds 5%, the devitrification resistance and chemical stability of the glass will deteriorate. Therefore, the content of K2O in the present invention is below 5%, and the content of K2O is preferably below 3%, more preferably below 2%. In some implementations, it can comprise about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% of K2O.
MgO can decrease the refractive index and melting temperature of the glass. However, in case of excessive MgO content, the refractive index of the glass will fail to meet the design requirements, and the devitrification resistance and stability of the glass will be reduced, and meanwhile the cost of the glass will rise. Therefore, the content of MgO is confined to 0˜8%, preferably 0-4%, more preferably 0-2%. In some implementations, it can comprise about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or 8% of MgO.
CaO helps to adjust the optical constant of the glass, improve the processing performance of the glass, and decrease the density of the glass. However, in case of excessive CaO content, the optical constant of the glass will fail to meet the design requirements, and the devitrification resistance will deteriorate. Therefore, the content of CaO is confined to 0-12%, preferably 1-9%, more preferably 3-7%. In some implementations, it can comprise about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5% or 12% of CaO.
In some implementations of the present invention, by controlling the ratio of the content of Na2O to the content of CaO, i.e., Na2O/CaO, to be below 5.0, it can increase the devitrification resistance of the glass. Therefore, Na2O/CaO is preferably below 5.0. Furthermore, by controlling Na2O/CaO within a range of 0.01-3.0. it is also conducive to increasing the light transmittance and Young's modulus of the glass. Therefore, Na2O/CaO is more preferably 0.01-3.0, and Na2O/CaO is further preferably 0.05-2.5. In some implementations of the present invention, the value of Na2O/CaO can be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9 or 5.0.
SrO can adjust the refractive index and Abbe number of the glass. However, if the content of SrO is excessive, the chemical stability of the glass will be decreased, and meanwhile the cost of the glass will also rise rapidly. Therefore, the content of SrO is confined to 0˜8%, preferably 0-4%, more preferably 0-2%. In some implementations, it can comprise about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7% 7.5% or 8% of SrO.
BaO is a necessary component for adjusting the refractive index and improving the transmittance and strength of the glass in the present invention. When the content of BaO is less than 15%, the above-mentioned effect is not obvious. The lower limit of the content of BaO is preferably 18%, and the lower limit of the content of BaO is more preferably 20%. On the other hand, if the content of BaO exceeds 35%, the devitrification resistance and chemical stability of the glass will become poor, and the density will increase significantly. Therefore, the upper limit of the content of BaO is 35%, preferably 32%; more preferably 30%. In some implementations of the present invention, it can comprise about 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5% or 35% of BaO.
In some implementations of the present invention, by controlling the ratio of the content of Nb2O5 to the content of BaO, i.e., Nb2O5/BaO, within a range of 0.2-1.2, the glass provided by the present invention can have excellent chemical stability, and meanwhile the thermal expansion coefficient of the glass can be decreased. Therefore, Nb2O5/BaO is preferably 0.2-1.2, and Nb2O5/BaO is more preferably 0.2-1.0. Furthermore, by controlling Nb2O5/BaO within a range of 0.25-0.9, it can also further increase the Young's modulus of the glass. Therefore, Nb2O5/BaO is further preferably 0.25-0.9, and Nb2O5/BaO is more further preferably 0.3-0.8. In some implementations of the present invention, the value of Nb2O5/BaO can be 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15 or 1.2.
ZrO2 can increase the refractive index of the glass and adjust the dispersion, and increase the devitrification resistance and strength of the glass. The present invention obtains the above-mentioned effect by comprising over 1% of ZrO2, preferably comprising over 2% of ZrO2. If the content of ZrO2 is higher than 10%, the melting difficulty of the glass will increase, the melting temperature will rise, and even inclusions and transmittance of the glass are likely to reduce in the glass. Therefore, the content of ZrO2 is below 10%, preferably below 8%, more preferably below 7%. In some implementations, it can comprise about 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10% of ZrO2.
In some implementations of the present invention, by controlling the ratio of the content of TiO2 to the total content of Nb2O5 and ZrO2 (Nb2O5+ZrO2), i.e., TiO2/(Nb2O5+ZrO2), within a range of 0.6-5.5, it is conductive to improving the devitrification resistance and light transmittance of the glass. Therefore, TiO2/(Nb2O5+ZrO2) is preferably 0.6-5.5, and TiO2/(Nb2O5+ZrO2) is more preferably 0.7-4.0. Furthermore, by controlling TiO2/(Nb2O5+ZrO2) within a range of 0.8-3.0, it can also make the glass obtain the appropriate abrasiveness and relative partial dispersion. Therefore, TiO2/(Nb2O5+ZrO2) is further preferably 0.8-3.0, and TiO2/(Nb2O5+ZrO2) is more further preferably 1.0-2.5. In some implementations of the present invention, the value of TiO2/(Nb2O5+ZrO2) can be 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4 or 5.5.
In some implementations of the present invention, by controlling the ratio of the total content of SiO2 and TiO2 (SiO2+TiO2) to the total content of Nb2O5, ZrO2, CaO and BaO (Nb2O5+ZrO2+CaO+BaO), i.e., (SiO2+TiO2)/(Nb2O5+ZrO2+CaO+BaO), within a range of 0.5-2.2, it can increase the glass-forming stability and chemical stability of the glass, and decrease the density of the glass. Therefore, (SiO2+TiO2)/(Nb2O5+ZrO2+CaO+BaO) is preferably 0.5-2.2, and (SiO2+TiO2)/(Nb2O5+ZrO2+CaO+BaO) is more preferably 0.6-2.0. Furthermore, by controlling (SiO2+TiO2)/(Nb2O5+ZrO2+CaO+BaO) within a range of 0.8-1.8, it can further increase the devitrification resistance of secondary compression and Young's modulus of the glass. Therefore, (SiO2+TiO2)/(Nb2O5+ZrO2+CaO+BaO) is further preferably 0.8-1.8, and (SiO2+TiO2)/(Nb2O5+ZrO2+CaO+BaO) is more further preferably 0.9-1.5. In some implementations of the present invention, the value of (SiO2+TiO2)/(Nb2O5+ZrO2+CaO+BaO) can be 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0, 2.05, 2.1, 2.15 or 2.2.
Ln2O3 (Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3) is a component for increasing the refractive index and chemical stability of the glass. By controlling the content of Ln2O3 to be below 10%, it can prevent the devitrification resistance of the glass from decrease. The upper limit of the content range of Ln2O3 is preferably 9%, more preferably 7%. In some implementations, Ln2O3 is preferably La2O3. In some implementations, it can comprise about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10% of Ln2O3.
In some implementations of the present invention, by controlling the total content of ZnO, SrO, and Ln2O3 (ZnO+SrO+Ln2O3) to the content of SiO2, i.e., (ZnO+SrO+Ln2O3)/SiO2, to be below 0.7, it is conductive to decreasing the density and relative partial dispersion of the glass. Therefore, (ZnO+SrO+Ln2O3)/SiO2 is preferably below 0.7, and (ZnO+SrO+Ln2O3)/SiO2 is more preferably below 0.6. Furthermore, the thermal expansion coefficient of the glass can be decreased by controlling (ZnO+SrO+Ln2O3)/SiO2 to be below 0.5. Therefore, (ZnO+SrO+Ln2O3)/SiO2 is further preferably below 0.5, and (ZnO+SrO+Ln2O3)/SiO2 is more further preferably below 0.3. In some implementations of the present invention, the value of (ZnO+SrO+Ln2O3)/SiO2 can be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.5, 0.55, 0.6, 0.65 or 0.7.
Al2O3 can improve the chemical stability of the glass. However, in case of excessive Al2O3, the devitrification resistance and melting performance of the glass will decrease. Therefore, the content of Al2O3 is below 5%, preferably below 3%, more preferably below 2%. In some implementations, it can comprise about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5% 4%, 4.5% or 5% of Al2O3.
In some implementations, the glass provided by the present invention can also comprise 0-1% of clarifying agent, in order to increase the de-foaming capability of the glass. Such clarifying agent includes, but is not limited to, one or more of Sb2O3, SnO2, SnO, and CeO2. Sb2O3 is preferably used as the clarifying agent. When the above-mentioned clarifying agents exist alone or in combination, the upper limit of the content of the clarifying agent is preferably 0.5%, more preferably 0.2%. In some implementations, the content of one or more of the above-mentioned clarifying agents is about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95% or 1%.
A small amount of other components not mentioned above can be added as required without impairing the glass characteristics of the present invention, such as P2O5, Bi2O3, Ta2O5, TeO2, and Ga2O3 (the individual or combined content of the above-mentioned components is preferably no more than 4%, more preferably no more than 2%, further preferably no more than 1%; the content of P2O5 is more further preferably 0%); and/or Bi2O3; and/or Ta2O5; and/or TeO2; and/or Ga2O3.
In the glass of the present invention, for the transition metal oxides such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo, even if they are contained in small amounts in a single or compound form, the glass could be colored and absorb at a specific wavelength in the visible light region, thereby impairing the properties of the present invention in increasing the visible light transmittance, and therefore, in particular, for optical glass with requirement on wavelength transmittance in the visible region, it is preferably not actually included.
Th, Cd, Tl, Os, Be and Se oxides have been used in a controlled manner as a harmful chemical substance in recent years, which is necessary not only in the glass manufacturing process, but also in the processing procedure and disposal after the productization for environmental protection measures. Therefore, in the case of attaching importance to the influence on the environment, it is preferably not actually included except for the inevitable incorporation. As a result, the optical glass does not actually contain a substance that contaminates the environment. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded even if a measure is not taken as a special environmental countermeasure. At the same time, in order to achieve environmental friendliness, the optical glass of the present invention preferably does not contain As2O3 and PbO.
The terms “not contained” and “0%” as used herein mean that the compound, molecule or element and the like are not intentionally added to the optical glass of the present invention as raw materials; however, as raw materials and/or equipment for the production of optical glass, there will be some impurities or components that are not intentionally added in small or trace amounts in the final optical glass, and this situation also falls within the protection scope of the present invention patent.
In the following paragraphs, the performance of optical glass provided in this invention will be described:
The refractive index (nd) and Abbe number (νd) of the optical glass is tested as per the method specified in GB/T 7962.1-2010.
In some implementations, the upper limit of the refractive index (nd) of the optical glass provided by the present invention is 1.96, preferably 1.95, more preferably 1.94.
In some implementations, the lower limit of the refractive index (nd) of the optical glass provided by the present invention is 1.89, preferably 1.90, more preferably 1.91.
In some implementations, the upper limit of the Abbe number (vd) of the optical glass provided by the present invention is 28, preferably 27, more preferably 26.
In some implementations, the lower limit of the Abbe number (vd) of the optical glass provided by the present invention is 20, preferably 21, more preferably 22.
The short-wave transmission spectrum characteristics of the glass provided by the present invention are represented by staining degree (λ70 and λ5). λ70 refers to a wavelength corresponding to a glass transmittance of 70%. The measurement of λ70 is carried out using a glass having a thickness of 10±0.1 mm with two opposing planes parallel to each other and optically polished, measuring the spectral transmittance in the wavelength region from 280 nm to 700 nm and a wavelength exhibiting 70% of the transmittance. The spectral transmittance or transmittance is an amount indicated by Iin in the case where the light of an intensity Iin is incident perpendicularly to the above surface of the glass, passes through the glass and passes an amount represented by Iout/Iin while emitting the light of an intensity Iout from a plane, and includes the transmittance of the surface reflection loss on the above surface of the glass. The higher the refractive index of the glass is, the greater the surface reflection loss becomes. Therefore, in the glass with high refractive index, a small value of λ70 means that the glass itself is colored very little and the light transmittance is high.
In some implementations, λ70 of the optical glass provided by the present invention is below 460 nm, λ70 is preferably below 450 nm, and λ70 is more preferably below 440 nm.
In some implementations, λ5 of the optical glass provided by the present invention is below 400 nm, as is preferably below 390 nm, and λ5 is more preferably below 380 nm.
The acid resistance stability (DA) (powder method) of the optical glass is tested as per the method specified in GB/T 17129.
In some implementations, the acid resistance stability (DA) of the optical glass provided by the present invention is above Class 2, preferably Class 1.
The water resistance stability (DW) (powder method) of the optical glass is tested as per the method specified in GB/T 17129.
In some implementations, the water resistance stability (DW) of the optical glass provided by the present invention is above Class 2, preferably Class 1.
The devitrification performance of the glass is measured by a temperature gradient furnace method which comprises the following steps: processing the glass into 180×10×10 mm samples, polishing lateral sides, placing the samples into a furnace having a temperature gradient (10° C./cm) and heating up to 1300° C. in the highest temperature zone, taking out the samples for cooling to room temperature after keeping the temperature for 4 hours, and observing the devitrification of the glass under a microscope, wherein the maximum temperature corresponding to the appearance of crystal in the glass is the upper limit of devitrification temperature of the glass.
In some implementations, the upper limit of devitrification temperature of the optical glass provided by the present invention is below 1200° C., preferably below 1160° C., more preferably below 1150° C., further preferably below 1140° C.
The Young's modulus (E) of the glass is tested by ultrasonic wave for P-wave velocity and S-wave velocity, and then calculated according to the following formula.
G=Vs2ρ
Wherein: E refers to Young's modulus, Pa;
In some implementations, Young's modulus (E) of the optical glass provided by the present invention is above 9000×107/Pa, preferably above 9500×107/Pa, more preferably above 10000×107/Pa, further preferably above 10500×107/Pa.
The thermal expansion coefficient (α100˜300° C.) of the optical glass is tested at 100-300° C. as per the method specified in GB/T 7962.16-2010.
The thermal expansion coefficient (α100˜300° C.) of the optical glass provided by the present invention is below 110×10−7/K, preferably below 105×10−7/K, more preferably below 100×10−7/K.
The density (ρ) of the optical glass is tested as per the method specified in GB/T7962.20-2010.
In some implementations, density (p) of the optical glass provided by the present invention is below 4.30 g/cm3, preferably below 4.20 g/cm3, more preferably below 4.10 g/cm3.
Abrasion degree (FA) of optical glass refers to the data obtained by the ratio of the abrasion quantity of sample to the abrasion quantity (volume) of the standard sample (H-K9 optical glass) multiplying by 100 with the formula below under exactly the same conditions:
Wherein: V—volume abrasion quantity of the tested sample;
In some implementations, abrasiveness (FA) of the optical glass provided by the present invention is above 150, preferably above 180, more preferably 200-300.
The relative partial dispersion of wavelengths x and y is expressed by the following formula (1):
According to the Abbe number formula, the following formula (2) is valid for most of the so-called “normal glass” (H-K6 and F4 are selected as the “normal glass” below).
This linear relationship is represented by Px,y as vertical coordinate and vd as horizontal coordinate, in which mx,y refers to the slope, and bx,y refers to the intercept.
As we all know, the correction of secondary spectrum, that is, achromatic for more than two wavelengths, requires at least one glass that does not conform to the above formula (2) (that is, its Px,y value deviates from the empirical formula of Abbe number), with deviation value expressed by ΔPx,y, and then each Px,y-vd point translates the quantity of ΔPx,y relative to the “normal line” conforming to the above formula (2). In this case, the ΔPx,y value of each glass can be calculated by the following formula (3):
Therefore, it can be known from the above that the calculation formula of the relative partial dispersion (Pg,F) is the following formula (4):
In some implementations, the relative partial dispersion (Pg,F) of the optical glass provided by the present invention is 0.6000-0.6500, preferably 0.6100-0.6400, more preferably 0.6150-0.6250.
The test method for devitrification resistance of secondary compression is as follows: cut the sample glass into 20×20×10 mm pieces, place into a muffle furnace with temperature as Tg+(200-250°) C for 15-30 minutes, then take out for cooling, and observe the surface and the inside for crystal or opacity. In case of no opacity and/or crystal in the glass sample, it means that the glass has excellent devitrification resistance of secondary compression.
The manufacturing method of the optical glass provided by the present invention is as follows: the glass of the present invention is made of conventional raw materials and processes, including but not limited to using oxide, hydroxide, fluoride, and various salts (carbonate, nitrate, sulfate, phosphate, and metaphosphate) as raw materials, mixing the ingredients according to the conventional method, and then feeding the mixed furnace burden into a 1000-1400° C. smelting furnace (e.g., platinum crucible) for melting, obtaining homogeneous molten glass without bubbles and undissolved substances after clarification and homogenization, shaping the molten glass in a mould, and performing annealing. Those skilled in the art can appropriately select raw materials, process methods and process parameters according to actual needs.
The glass preform can be made from the optical glass formed by, for example, direct drop forming, grinding or thermoforming, and other compression molding means. That is to say, the precision glass preform can be made by direct precision drop molding of molten optical glass, or glass preform can be made by grinding and other machining methods, or the glass preform can be made by making a preform for compression molding with the optical glass, re-thermoforming this preform, and then grinding the preform. It should be noted that the means for preparing glass preform is not limited to the above means.
As mentioned above, the optical glass of the present invention is useful for various optical elements and optical designs, wherein the particularly preferred method is to form a preform by the optical glass of the present invention, and use this preform for re-thermoforming, precision stamping and the like to make optical elements such as lens and prism.
The glass preform and the optical element of the present invention are both formed by the optical glass of the present invention described above. The glass preform of the present invention has excellent characteristics of the optical glass; the optical element of the present invention has excellent characteristics of the optical glass, and can provide such optical elements as a variety of lenses and prisms having a high optical value.
Examples of the lens include various lenses with spherical or aspheric surfaces, such as concave meniscus lens, convex meniscus lens, biconvex lens, biconcave lens, planoconvex lens and planoconcave lens.
The optical element formed by the optical glass of the present invention can make optical instruments such as photographic equipment, camera equipment, projector equipment, display equipment, on-board equipment and monitoring equipment.
The following non-limiting embodiments are provided in order to further clearly explain and illustrate the technical solution of the present invention.
This embodiment obtains the optical glass with composition as shown in Table 1-Table 4 by the manufacturing method of the above-mentioned optical glass. In addition, the characteristics of each glass are measured by the test method described in the present invention, and the measurement results are shown in Tables 1 to 4. In the devitrification resistance test of secondary compression in Tables 1 to 4, according to the aforesaid test method, the glass without opacity and crystal particle on the surface and inside is denoted as “A”, the glass without opacity and crystal particle inside, but with devitrification particle on the surface, is denoted as “B” (the devitrification particle on the surface of the glass can be removed by grinding during secondary compression, but the grinding cost will be increased, so the glass without devitrification particle inside and outside is more preferably selected), the glass without opacity, but with 1-10 crystal particles inside, is denoted as “C”, the glass without opacity, but with 10-20 crystal particles inside, is denoted as “D”, and the glass with opacity or dense devitrification particles inside is denoted as
The glass obtained by Embodiments 1-23 of the optical glass is made into a variety of lenses and prisms and other preforms such as concave meniscus lens, convex meniscus lens, biconvex lens, biconcave lens, planoconvex lens, and planoconcave lens by means of, for example, grinding, or re-thermoforming, precision stamping and other compression molding methods.
The preforms obtained in the above-mentioned glass preform embodiment are annealed for fine-tuning while reducing the deformation inside the glass, so that the optical characteristics such as the refractive index are brought to the desired values.
Then, each of the preforms is ground and polished, and a variety of lenses and prisms such as concave meniscus lens, convex meniscus lens, biconvex lens, biconcave lens, planoconvex lens, and planoconcave lens are prepared. An anti-reflection film may be coated on the surface of the obtained optical element.
Through optical design and the use of one or more optical elements to form optical component or optical assembly, the optical element prepared by the above-mentioned optical element embodiment can be used, for example, in imaging device, sensor, microscope, medical technology, digital projection, communication, optical communication technology/information transmission, optics/lighting in the automobile field, photolithography, excimer laser, wafer, computer chip, and integrated circuit and electronic device including such circuit and chip, or camera device and apparatus used in the field of on-board products.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202111047093.X | Sep 2021 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2022/112977 | 8/17/2022 | WO |
