CN109502964B - Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof - Google Patents
Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof Download PDFInfo
- Publication number
- CN109502964B CN109502964B CN201811493174.0A CN201811493174A CN109502964B CN 109502964 B CN109502964 B CN 109502964B CN 201811493174 A CN201811493174 A CN 201811493174A CN 109502964 B CN109502964 B CN 109502964B
- Authority
- CN
- China
- Prior art keywords
- glass
- tio
- lanthanum flint
- sio
- heavy lanthanum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (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)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses heavy lanthanum flint glass, a prefabricated member thereof, an optical element and an optical instrument. The heavy lanthanum flint glassContains the following components in percentage by weight: siO 2 2 ：12‑30％，Ln 2 O 3 :10-25%, the Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 In total amount of TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 ：10.5‑40％，B 2 O 3 :0-10%, RO:20-35%, wherein the RO is one or more of BaO, caO, mgO and SrO, and ZrO 2 :0.5-10%, wherein (SiO) 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) Is 1-30. The glass has the refractive index (nd) of 1.86-1.92 and the Abbe number (vd) of 25-30, can meet the optical performance required by a precision instrument, has excellent anti-devitrification performance and low temperature coefficient of the refractive index, and can effectively reduce thermal aberration caused by temperature difference.
Description
Technical Field
The invention belongs to the field of optical glass, and particularly relates to heavy lanthanum flint glass, a prefabricated member thereof, an optical element and an optical instrument.
Background
Heavy lanthanum flint glass with refractive index (nd) of 1.86-1.92 and Abbe number (vd) of 25-30 is widely applied to lenses of precision optical instruments, and the heavy lanthanum flint glass can meet the requirements of modern precision compression molding forming technology, but the temperature coefficient of the refractive index of the existing heavy lanthanum flint glass is higher.
The refractive index of the optical glass is a function of temperature, and the change of the refractive index caused by unit temperature, namely the temperature coefficient of the refractive index of the glass is a key performance parameter for measuring the influence of temperature on the refractive index of the optical glass.
In optical instruments used in the fields of medical treatment, night photography, integrated circuit lithography and the like, the temperature of the use environment of an optical lens is continuously increased along with the increase of the use time, the refractive index of glass is greatly changed along with the increase of the use environment, the imaging quality of the glass is seriously reduced, and the resolution of a system is further influenced. The thermal aberration compensation technology is often adopted for compensation, for example, a photoetching objective lens of a photoetching machine is compensated through a movable lens combination, a thermal aberration compensation element and the like, but the technology has higher thresholds and is only mastered by a few manufacturers in the world, so that the popularization and the application of the related technology are greatly restricted, the market competition is not facilitated, and the situation that a precision instrument is expensive is broken through.
In addition, the existing heavy lanthanum flint glass has higher crystallization upper limit temperature, poor stability during high-temperature processing and large difficulty of a hot processing technology, so that the application range of the glass is limited.
In addition, the current heavy lanthanum flint glass with high density and high tinting strength cannot meet the requirements of people on light and small instruments and equipment and high transmittance.
Therefore, it is necessary to develop a heavy lanthanum flint glass having high transmittance, high image quality, excellent temperature coefficient of refractive index, and low crystallization upper limit temperature.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide heavy lanthanum flint glass, the refractive index (nd) of the glass is 1.86-1.92, the Abbe number (vd) is 25-30, the optical performance required by a precision instrument can be met, the devitrification resistance is excellent, the temperature coefficient of the refractive index is low, and the thermal aberration caused by temperature difference can be effectively reduced.
The invention further provides a prefabricated member, an optical element and an optical instrument which are made of the heavy lanthanum flint glass.
The technical scheme adopted by the invention for realizing the purpose is as follows:
heavy lanthanum flint glass, comprising, in weight%: siO 2 2 ：12-30％，Ln 2 O 3 :10-25%, ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 In total amount of (3), tiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 ：10.5-40％，B 2 O 3 :0-10%, RO:20-35%, wherein the RO is one or more of BaO, caO, mgO and SrO, and ZrO 2 :0.5-10%, wherein (SiO) 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) Is 1-30.
Further, the heavy lanthanum flint glass further comprises, in weight%: rn 2 O:0-8%, the Rn 2 O is Li 2 O、Na 2 O and K 2 One or more of O, sb 2 O 3 ：0-1％，ZnO：0-7％，Ta 2 O 5 ：0-10％，Al 2 O 3 ：0-10％。
Heavy lanthanum flint glass consists of SiO 12-30 wt% 2 10-25% Ln 2 O 3 Said Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 10.5-40% of TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 20-35% of RO, wherein the RO is one or more of BaO, caO, mgO and SrO, and 0.5-10% of ZrO 2 0-10% of B 2 O 3 0-8% of Rn 2 O, the Rn 2 O is Li 2 O、Na 2 O and K 2 One or more of O, 0-1% of Sb 2 O 3 0-7% of ZnO,0-10% of Ta 2 O 5 And 0-10% of Al 2 O 3 Composition of wherein (SiO) 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) Is 1-30.
Further, the content of each component of the heavy lanthanum flint glass meets one or more of the following 4 conditions:
1)B 2 O 3 /TiO 2 greater than 0 and equal to or less than 1;
2)BaO/B 2 O 3 greater than 0 and equal to or less than 70;
3)(La 2 O 3 +TiO 2 +ZrO 2 )/SiO 2 0.7 to 6;
4)(SiO 2 +La 2 O 3 +ZrO 2 )/TiO 2 is 0.75-6.5.
Further, the aforementioned heavy lanthanum flint glass, wherein: siO 2 2 :15-25%, and/or Ln 2 O 3 :12-22%, and/or TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 :17-33%, and/or RO:22-32%, and/or ZrO 2 :2-8%, and/or B 2 O 3 :0.5-6%, and/or Rn 2 O:0.5-6%, and/or Sb 2 O 3 :0-0.5%, and/or ZnO:0-5%, and/or Ta 2 O 5 :0-5%, and/or Al 2 O 3 ：0-5％。
Further, the content of each component of the heavy lanthanum flint glass meets one or more than one of the following 5 conditions:
1)B 2 O 3 /TiO 2 0.02-0.4;
2)BaO/B 2 O 3 is 3.6 to 64;
3)(La 2 O 3 +TiO 2 +ZrO 2 )/SiO 2 1.2-5;
4)(SiO 2 +La 2 O 3 +ZrO 2 )/TiO 2 1.1-3.7;
5)(SiO 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) Is 2.15-20.
Further, the content of each component of the heavy lanthanum flint glass meets one or two of the following 2 conditions:
6)SiO 2 +TiO 2 30 to 50 percent;
7)B 2 O 3 /SiO 2 is 0.02-0.4.
Further, the aforementioned heavy lanthanum flint glass, wherein: siO 2 2 :18-23%, and/or Ln 2 O 3 :13-18%, and/or TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 :22-31%, and/or RO:23-30%, and/or ZrO 2 :2-6%, and/or B 2 O 3 :1-4%, and/or Rn 2 O:1-5%, and/or Sb 2 O 3 :0-0.2%, and/or ZnO:0-3%, and/or does not contain Ta 2 O 5 And/or does not contain Al 2 O 3 。
Further, the content of each component of the heavy lanthanum flint glass meets one or more than one of the following 5 conditions:
1)B 2 O 3 /TiO 2 0.02-0.23;
2)BaO/B 2 O 3 is 5 to 30;
3)(La 2 O 3 +TiO 2 +ZrO 2 )/SiO 2 1.5 to 4;
4)(SiO 2 +La 2 O 3 +ZrO 2 )/TiO 2 1.2-2;
5)(SiO 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) Is 3.36-12.
Further, the content of each component of the heavy lanthanum flint glass meets one or two of the following 2 conditions:
6)SiO 2 +TiO 2 37 to 50 percent;
7)B 2 O 3 /SiO 2 is 0.02-0.34.
Further, the aforementioned heavy lanthanum flint glass, wherein: tiO 2 2 :10-30%, and/or Nb 2 O 5 :0.5-10%; preferably, tiO 2 :15-25%, and/or Nb 2 O 5 :2 to 8 percent; more preferably, tiO 2 :19-24%, and/or Nb 2 O 5 ：3-7％。
Further, the aforementioned heavy lanthanum flint glass, wherein: la 2 O 3 :10-25%, and/or BaO:20-35%, and/or Na 2 O:0 to 8 percent; preferably, la 2 O 3 :12-22%, and/or BaO:22-32%, and/or Na 2 O:0.5 to 6 percent; more preferably, la 2 O 3 :13-18%, and/or BaO:23-30%, and/or Na 2 O：1-5％。
Further, the lambda value of the heavy lanthanum flint glass 70 450nm or less, preferably 440nm or less, more preferably 430nm or less; λ thereof 5 390nm or less, preferably 385nm or less, more preferably 380nm or less; the density (. Rho.) was 4.5g/cm 3 Hereinafter, it is preferably 4.3g/cm 3 Hereinafter, more preferably 4.25g/cm 3 The following; the upper limit temperature of crystallization is 1200 ℃ or lower, preferably 1180 ℃ or lower; temperature coefficient of refractive index of 2.4X 10 -6 /. Degree.C.or less, preferably 2.3X 10 -6 Lower than/° C。
Further, the refractive index (nd) of the heavy lanthanum flint glass is 1.86 to 1.92, preferably 1.86 to 1.91, and more preferably 1.87 to 1.90; an Abbe number (vd) of 25 to 30, preferably 25 to 29, more preferably 26 to 29.
Further, the transition temperature (T) of the heavy lanthanum flint glass g ) Is 720 ℃ or lower, preferably 710 ℃ or lower, more preferably 705 ℃ or lower; stability against Water action (D) W ) Is 2 or more, preferably 1; stability against acid action (D) A ) Is 2 or more, preferably 1. The glass prefabricated member is made of the heavy lanthanum flint glass.
The optical element is made of the heavy lanthanum flint glass or the glass prefabricated member.
The optical instrument is made of the optical element.
The invention has the beneficial effects that: through reasonable component proportion, the heavy lanthanum flint glass has excellent temperature coefficient of refractive index, crystallization upper limit temperature and lambda while ensuring the required refractive index and Abbe number 70 、λ 5 And chemical stability, and the like, and is suitable for popularization and application in precision instruments requiring high transmittance, high imaging quality and small thermal aberration.
Detailed Description
Heavy lanthanum flint glass
The composition of the heavy lanthanum flint glass is explained in detail below, and when not specifically stated, the content and the total content of each glass component mean the weight content, expressed in weight percent, which is the percentage of the weight of a certain component or the sum of the weights of several components in the total weight of the optical glass; the ratio of the glass components or the sum of the components is the ratio of the corresponding weight contents or the ratio of the sum of the weight contents.
The heavy lanthanum flint glass comprises the following components in percentage by weight: siO 2 2 ：12-30％，Ln 2 O 3 :10-25%, the Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 In total of (A) containsAmount of TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 ：10.5-40％，B 2 O 3 0-10%, RO:20-35%, wherein the RO is one or more of BaO, caO, mgO and SrO, and ZrO 2 :0.5-10%, wherein (SiO) 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) Is 1-30.
In the glass of the invention, siO 2 Is a network former of glass and is a main component constituting a glass skeleton. SiO 2 2 The content is closely related to the devitrification resistance, transmittance, refractive index and dispersion of the glass. If the content of the glass is less than 12 percent, the refractive index and the dispersion of the glass cannot reach the design expectation, and meanwhile, the anti-crystallization performance and the transmittance of the glass are greatly reduced; if the content is more than 30%, the solubility and devitrification resistance of the glass may be deteriorated, and the refractive index and dispersion may not be as designed. Therefore, in the present invention, siO 2 The content of (B) is set to 12 to 30%, preferably 15 to 25%, and more preferably 18 to 23%.
B 2 O 3 And also a glass network forming component, are optional components in the present invention. In some embodiments of the invention, B is introduced 2 O 3 Glass meltability and devitrification resistance can be improved, but when the incorporation amount thereof exceeds 10%, glass forming stability is lowered and refractive index is lowered, and therefore, B of the present invention 2 O 3 The content of (b) is set to 0 to 10%, preferably 0.5 to 6%, and more preferably 1 to 4%.
SiO 2 And B 2 O 3 As two glass network components, the glass has unique functions and mutually restricts and influences the glass forming stability and the glass transition temperature (T) of the glass g ) When B is 2 O 3 /SiO 2 A ratio higher than 0.4, a glass transition temperature (T) g ) Is deteriorated when B 2 O 3 /SiO 2 When the ratio is less than 0.02, the glass forming stability is lowered. Thus, in some of the present invention, B is contained 2 O 3 In the heavy lanthanum flint glass embodiment of (1), B 2 O 3 /SiO 2 The ratio is set to 0.02-0.4, more preferably0.02-0.34。
Rare earth oxide Ln 2 O 3 (La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 ) It contributes to increase of the refractive index of the glass, and when the total content thereof is less than 10%, the desired optical constants cannot be obtained, but when the total content thereof exceeds 25%, the chemical stability, resistance to devitrification of the glass will be reduced, and the raw material cost of the glass will be increased. Thus La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 Total content Ln of (2) 2 O 3 The content is set to 10 to 25%, preferably 12 to 22%, and more preferably 13 to 18%. In some embodiments, the rare earth oxides of the present invention may comprise from 10 to 25% La 2 O 3 Preferably 12-22% La 2 O 3 More preferably 13-18% La 2 O 3 The refractive index of the glass is further improved, the transmittance of a visible light wave band is improved, the temperature coefficient of the refractive index of the glass is reduced, and the devitrification resistance is improved.
Due to TiO 2 、Nb 2 O 5 、WO 3 、Bi 2 O 3 All have the effect of increasing the refractive index but also the dispersion, when TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 When the content exceeds 40%, the glass dispersion is remarkably increased, the glass coloring tendency is increased, and the transmittance is also decreased, so that TiO is added 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 The upper limit of (3) is set to 40%, the preferable upper limit is 33%, and the more preferable upper limit is 31%. However, when TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 Since too low a content will cause a decrease in thermal stability and press formability of the glass, the lower limit thereof is set to 10.5%, preferably 17%, and more preferably 22%.
In the heavy lanthanum flint glass of the present invention, tiO is preferably used 2 And Nb 2 O 5 To obtain better refractive index and abbe number. Adding more than 10% of TiO 2 Into the glass of the inventionCan participate in the formation of glass network, increase the crystallization resistance stability of the glass, and can partially replace expensive Nb 2 O 5 、WO 3 、Bi 2 O 3 However, a content higher than 30% leads to a decrease in glass transmittance and an increase in glass coloring tendency; nb 2 O 5 The proper introduction of the rare earth element can lead the glass to be more stable and improve the devitrification resistance, and therefore, in the heavy lanthanum flint glass, tiO is added 2 Is set to 10-30%, preferably 15-25%, more preferably 19-24%; mixing Nb with 2 O 5 The content is set to 0.5 to 10%, preferably 2 to 8%, more preferably 3 to 7%.
Further, the inventor researches to find that the component B 2 O 3 And TiO 2 Ratio B of 2 O 3 /TiO 2 Will influence the lambda of the glass 70 、λ 5 Crystallization upper limit temperature and refractive index temperature coefficient, when the ratio B 2 O 3 /TiO 2 When the temperature is more than 1, the crystallization upper limit temperature is increased and the temperature coefficient of the refractive index is increased. In the present invention, it is preferable that B is a group B for obtaining an optical glass having excellent properties such as higher transmittance 2 O 3 /TiO 2 Greater than 0 and not greater than 1, more preferably B 2 O 3 /TiO 2 Is 0.02 to 0.4, and B is more preferably 2 O 3 /TiO 2 Is 0.02-0.23.
SiO 2 And TiO 2 The total content of (2) is a total of λ of glass 70 、λ 5 Stability to water (D) W ) And stability against acid action (D) A ) Has an important influence when SiO is used 2 +TiO 2 When the content of (D) is more than 50%, the transmittance in the visible light region of the glass is lowered, the coloring is increased, and the water resistance stability is improved (D) W ) And stability against acid action (D) A ) Decrease but when SiO 2 +TiO 2 When the content of (B) is less than 30%, glass forming stability is deteriorated and thermal expansion coefficient is increased. Therefore, in the present invention, siO is preferable 2 +TiO 2 Is 30 to 50%, more preferably 37 to 50%.
Furthermore, the inventors found that when the ratio (SiO) 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) When the glass content is less than 1, the glass stability is poor, the crystallization upper limit temperature is increased, the refractive index temperature coefficient is increased, the thermal aberration is large, the glass specific gravity is increased, and the purpose of light weight is difficult to achieve; however, when the ratio is more than 30, the glass transmittance is decreased and the coloring tendency is remarkably increased. Therefore, the ratio (SiO) 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) Defined as a ratio (SiO) of 1 to 30, more preferably 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) Is 2.15-20, and a further preferable ratio (SiO) 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) Is 3.36-12.
RO belongs to alkaline earth metal oxide and is one or more of CaO, mgO, srO and BaO. In the heavy lanthanum flint glass, more than 20 percent of alkaline earth metal oxide can improve the Young modulus of the glass, reduce the high-temperature viscosity of the glass, balance the components of the glass and improve the melting performance of the glass. However, when the total content of RO is more than 35%, the excessive alkaline earth metal oxide may lower the devitrification resistance of the glass. Therefore, the present invention sets the value of RO to 20 to 35%, preferably 22 to 32%, more preferably 23 to 30%. In some embodiments, the alkaline earth metal oxide of the present invention may comprise 20 to 35% of BaO, preferably 22 to 32% of BaO, and more preferably 23 to 30% of BaO, to further reduce the temperature coefficient of refractive index of the glass, to improve the devitrification resistance and chemical stability of the glass.
In some embodiments, baO and B 2 O 3 The addition ratio of (A) to (B) is stable to the glass refractive index temperature coefficient and water resistance (D) W ) And stability against acid action (D) A ) There is an important impact. When BaO/B 2 O 3 When the amount is more than 0, the glass has improved meltability, and the temperature coefficient of refractive index of the glass can be lowered to reduce thermal aberration, but when BaO/B is used 2 O 3 When the amount is more than 70, the stability of the glass against the action of acid and water and the devitrification resistance are lowered. Thus, baO/B 2 O 3 Is set to more than 0 and 70 or less, preferably BaO/B 2 O 3 Is 3.6 to 64, more preferably BaO/B 2 O 3 Is 5-30.
ZrO 2 The component is an essential component in the invention, is a high-refraction low-dispersion oxide, and the content of ZrO is more than 0.5 percent 2 Can raise the refractive index of the glass and adjust the dispersion. Meanwhile, the devitrification resistance and the chemical stability of the glass can be improved. However, if the content of the heavy lanthanum flint glass is more than 10%, the glass is difficult to melt, the melting temperature is increased, and inclusions in the glass and the transmittance of the glass are easily reduced. Therefore, the content thereof is set to 0.5 to 10%, preferably 2 to 8%, and more preferably 3 to 7%.
ZrO 2 In the glass of the invention with the component La 2 O 3 、SiO 2 、TiO 2 Commonly adjusting nd, vd, lambda of the glass 70 、λ 5 And the crystallization upper limit temperature and the temperature coefficient of the refractive index. The inventor confirms through experiments that when the ratio (La) is used 2 O 3 +TiO 2 +ZrO 2 )/SiO 2 Regulation of nd, vd, lambda 70 、λ 5 In the case where the ratio is in the range of 0.7 to 6, and the value is less than 0.7, the glass will be poor in meltability, poor in stability and low in refractive index; when (La) 2 O 3 +TiO 2 +ZrO 2 )/SiO 2 When the content is more than 6, the transmittance in the visible light region of the glass is lowered, and the degree of coloration is deteriorated. More preferably (La) 2 O 3 +TiO 2 +ZrO 2 )/SiO 2 Is in the range of 1.2 to 5, most preferably in the range of 1.5 to 4. When the ratio (SiO) 2 +La 2 O 3 +ZrO 2 )/TiO 2 Adjusting lambda of glass 70 、λ 5 A preferable range of the ratio of the upper limit temperature of crystallization to the temperature coefficient of refractive index is 0.75 to 6.5, and when the value is 6.5 or less, more excellent optical transmission performance and more excellent anti-crystallization performance can be obtained; however, when the value is less than 0.75 or more than 6.5, it will be difficult to maintain the temperature coefficient of refractive index at 2.4X 10 -6 Below/° c, both the optical properties and the devitrification resistance were significantly deteriorated. As a more preferable embodiment, the ratio (SiO) 2 +La 2 O 3 +ZrO 2 )/TiO 2 Is in the range of 1.1 to 3.7, with the most preferred range being 1.2 to 2.
Rn 2 O is an alkali metal oxide, being Li 2 O、Na 2 O、K 2 One or more of O, are optional components in the present invention. In the glass system of the present invention, the desired high temperature viscosity can be obtained by an appropriate amount of alkali metal oxide, and at the same time, when an appropriate amount of alkali metal oxide is mixed with B 2 O 3 In coexistence, B can be increased 2 O 3 The compactness of the network can obtain better light transmittance. However, too much alkali metal oxide may drastically deteriorate the devitrification resistance of the glass. Therefore, in the present invention, rn 2 The value of O is set to 0 to 8%, preferably 0.5 to 6%, more preferably 1 to 5%. In some embodiments, 0-8% Na may be included in the alkali metal oxides of the present invention 2 O, preferably 0.5-6% Na 2 O, more preferably 1-5% Na 2 O, further lowering the glass transition temperature and improving the melting property of the glass.
ZnO can adjust the refractive index and dispersion of glass, improve the devitrification resistance of the glass, reduce the transition temperature of the glass and improve the chemical stability of the glass. ZnO can also reduce the high-temperature viscosity of the glass, so that the glass can be smelted at a lower temperature, and the transmittance of the glass can be improved. However, if the amount of ZnO added is too large, the devitrification resistance of the glass is rather lowered, and the high-temperature viscosity is small, which makes molding difficult. In the glass system of the present invention, znO is an optional component and is contained in an amount of 0 to 7%, preferably 0 to 5%, more preferably 0 to 3%.
Ta 2 O 5 Can function to increase the refractive index and reduce dispersion, and is an optional component in the heavy lanthanum flint glass of the present invention in an amount of 0 to 10%, preferably 0 to 5%. Because it is expensive, it is more preferable not to contain Ta 2 O 5 。
Al 2 O 3 The thermal expansion coefficient of the glass can be reduced, and the thermal stability of the glass is improved. However, high Al 2 O 3 The concentration generally reduces the liquidus viscosity of the glass. In the inventionIn (b), the content is set to 0 to 10%, preferably 0 to 5%, and more preferably Al is not contained 2 O 3 。
In addition, 0 to 1%, preferably 0 to 0.5% of a refining agent Sb may be introduced into the heavy lanthanum flint glass of the present invention 2 O 3 。
Other components not mentioned above, such as P, can be added in small amounts as required within the range not impairing the characteristics of the glass of the present invention 2 O 5 、TeO 2 、GeO 2 、Lu 2 O 3 And so on. However, since the glass is colored and absorbs at a specific wavelength in the visible light region even when a small amount of a transition metal component such as V, cr, mn, fe, co, ni, cu, ag, and Mo is contained alone or in combination, thereby reducing the property of the present invention to improve the effect of the visible light transmittance, it is preferable that the optical glass, which requires transmittance at a wavelength in the visible light region, is not substantially contained.
In recent years, compounds of Pb, as, th, cd, tl, os, be, and Se tend to Be used As harmful chemicals under control, and measures for protecting the environment are required not only in the glass production process but also in the processing process and in handling after the production of products. Therefore, when importance is attached to the influence on the environment, it is preferable that these components are not substantially contained except for inevitable mixing. 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 disposed of without taking special measures for environmental measures.
"not including", "0%" in the present invention means that the compound, molecule or element is not intentionally added as a raw material to the heavy lanthanum flint 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 heavy lanthanum flint glass.
As can be seen from the above, in the glass system of the present invention, one component may have an effect on multiple properties of the glass. The optimization of one property with the same component may lead to the deterioration of another property, and thus the synergy and mutual control of the various components in the entire glass system is important. The inventor of the invention obtains the heavy lanthanum flint glass at nd, vd and lambda through experimental study 70 、λ 5 Rho, upper limit temperature of crystallization, temperature coefficient of refractive index, D W 、D A Glass forming stability or transition temperature (T) g ) And the like.
The heavy lanthanum flint glass or the product thereof has various performance indexes tested by the following method:
[ refractive index ]
The refractive index (nd) was measured according to GB/T7962.1-2010 method.
[ Abbe number ]
The Abbe number (vd) was measured according to the GB/T7962.1-2010 method.
[ coloring of glass ]
λ 70 The wavelength corresponding to the transmittance of the glass of 70% is indicated, and λ 5 is the wavelength corresponding to the transmittance of the glass of 5%. Wherein λ is 70 Is measured using a glass having a thickness of 10 + -0.1 mm with two opposing planes parallel to each other and optically polished, measuring a spectral transmittance in a wavelength region from 280nm to 700nm and exhibiting a wavelength of transmittance of 70%.
[ temperature coefficient of refractive index ]
The temperature coefficient of the refractive index is tested according to the method specified in GB/T7962.4-2010, and the temperature coefficient of the refractive index of 20-40 ℃ is measured.
[ transition temperature of glass ]
Transition temperature (T) of glass g ) Measured according to the method specified in GB/T7962.16-2010, the unit: DEG C.
[ upper limit temperature of crystallization ]
The crystallization upper limit temperature test method comprises the following steps: measuring the crystallization performance of the glass by adopting a temperature gradient furnace method, manufacturing the glass into a sample of 180 x 10mm, polishing the side surface, putting the sample into a furnace with a temperature gradient (5 ℃/cm), heating to 1400 ℃, keeping the temperature for 4 hours, taking out the sample, naturally cooling to room temperature, observing the crystallization condition of the glass under a microscope, wherein the highest temperature corresponding to the occurrence of crystals of the glass is the crystallization upper limit temperature of the glass. The lower the crystallization upper limit temperature of the glass is, the stronger the stability of the glass at high temperature is, and the better the production process performance is.
[ chemical stability ]
Stability to Water action (D) W ) Testing according to GB/T17129.
Stability against acid action (D) A ) Testing according to GB/T17129.
[ Density ]
The density (. Rho.) was measured according to GB/T7962.20-1987 Density test method for colorless optical glass.
Through tests, the heavy lanthanum flint glass has the following properties: a refractive index (nd) of 1.86 to 1.92, preferably 1.86 to 1.91, more preferably 1.87 to 1.90; an Abbe number (vd) of 25 to 30, preferably 25 to 29, more preferably 26 to 29; transition temperature (T) g ) Is 720 ℃ or lower, preferably 710 ℃ or lower, more preferably 705 ℃ or lower; lambda [ alpha ] 70 450nm or less, preferably 440nm or less, more preferably 430nm or less; lambda 5 390nm or less, preferably 385nm or less, more preferably 380nm or less; the density (. Rho.) was 4.5g/cm 3 Hereinafter, it is preferably 4.3g/cm 3 Hereinafter, more preferably 4.25g/cm 3 The following; stability against Water action (D) W ) Is 2 or more, preferably 1; stability against acid action (D) A ) Is 2 or more, preferably 1; the upper limit temperature of crystallization is below 1200 ℃, preferably below 1180 ℃; temperature coefficient of refractive index of 2.4X 10 -6 /. Degree.C.or less, preferably 2.3X 10 -6 Below/° c.
Next, the glass preform, the optical element and the optical instrument of the present invention are described.
The glass preform and the optical element of the present invention are both formed of the heavy lanthanum flint glass of the present invention described above. The glass prefabricated member has the characteristics of high refractive index and lower temperature coefficient of refractive index; the optical element of the present invention has high refractive index and low temperature coefficient of refractive index characteristics, and can provide various optical elements such as 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.
Further, since the prism has a relatively high refractive index, by combining the prism with an imaging optical system and bending the optical path to direct the prism in a desired direction, a compact and wide-angle optical system can be realized.
The optical element formed by the optical glass can be used for manufacturing optical instruments such as photographic equipment, camera equipment, display equipment, monitoring equipment and the like.
[ examples of heavy lanthanum flint glasses ]
In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.
In order to obtain glasses having compositions shown in tables 1 to 6, carbonates, nitrates, hydroxides, oxides, boric acid, etc. were used as raw materials, raw materials corresponding to the optical glass components were weighed in proportion, mixed thoroughly to obtain a blended raw material, the blended raw material was put into a platinum crucible, heated to 1200 to 1450 ℃, melted, stirred, and clarified to form a uniform molten glass, and the molten glass was appropriately cooled, poured into a preheated mold, kept at 650 to 700 ℃ for 2 to 4 hours, and then slowly cooled to obtain 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 6.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
TABLE 7
[ glass preform examples ]
The heavy lanthanum flint glasses obtained in examples 1 to 36 were cut into a predetermined size, and then a release agent was uniformly applied to the surface of the glass, followed by heating, softening, and press molding to prepare preforms of various lenses and prisms 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. Alternatively, a preform for precision press molding was formed using the heavy lanthanum flint glass obtained in examples 1 to 36, and then precision press molding was performed to form a lens or a prism, thereby producing a preform.
[ optical element examples ]
The preforms obtained in the above examples of glass preforms were annealed to reduce the deformation in the glass and to fine-tune the optical properties such as refractive index to 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 further coated with an antireflection film.
[ optical instrument example ]
The optical element obtained by the above-described optical element embodiment is used for, for example, an imaging device, a sensor, a microscope, a medical technology, a digital projection, a communication, an optical communication technology/information transmission, an optical/illumination in an automobile field, a lithography technology, an excimer laser, a wafer, a computer chip, and an integrated circuit and an electronic device including such a circuit and a chip, by forming an optical component or an optical assembly by using one or more optical elements through an optical design, and particularly, is used for an imaging device and an apparatus in an in-vehicle field.
Claims (26)
1. Heavy lanthanum flint glass, characterized in that it comprises, in weight%: siO 2 2 ：12-30％，Ln 2 O 3 :16-25%, said Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 The total content of La 2 O 3 ：15-25％，TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 ：10.5-40％，B 2 O 3 :0-10%, RO:20-35%, wherein the RO is one or more of BaO, caO, mgO and SrO, and ZrO 2 :0.5-10%, wherein (SiO) 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) Is 3.15 to 30, (SiO) 2 +La 2 O 3 +ZrO 2 )/TiO 2 Is 0.75-6.5.
2. The heavy-lanthanum flint glass according to claim 1, further comprising, in weight%: rn 2 O:0-8%, the Rn 2 O is Li 2 O、Na 2 O and K 2 One or more of O, sb 2 O 3 ：0-1％，ZnO：0-7％，Ta 2 O 5 ：0-10％，Al 2 O 3 ：0-10％。
3. Heavy lanthanum flint glass, characterized in that it consists, in% by weight, of 12 to 30% SiO 2 16-25% Ln 2 O 3 Said Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 The total content of La 2 O 3 :15-25% of TiO and 10.5-40% of TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 20-35% of RO, wherein the RO is BaO,One or more of CaO, mgO and SrO, and 0.5-10% of ZrO 2 0-10% of B 2 O 3 0-8% of Rn 2 O, the Rn 2 O is Li 2 O、Na 2 O and K 2 One or more of O, 0-1% of Sb 2 O 3 0-7% of ZnO,0-10% of Ta 2 O 5 And 0-10% of Al 2 O 3 Composition of wherein (SiO) 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) Is 3.15-30.
4. The heavy lanthanum flint glass according to any one of claims 1 to 3, wherein the content of each component satisfies one or more of the following 4 conditions:
1)B 2 O 3 /TiO 2 greater than 0 and equal to or less than 1;
2)BaO/B 2 O 3 greater than 0 and equal to or less than 70;
3)(La 2 O 3 +TiO 2 +ZrO 2 )/SiO 2 is 0.7-6.
5. The heavy lanthanum flint glass of any one of claims 1 to 3, wherein: siO 2 2 :15-25%, and/or Ln 2 O 3 :16-22%, and/or La 2 O 3 :15-22%, and/or TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 :17-33%, and/or RO:22-32%, and/or ZrO 2 :2-8%, and/or B 2 O 3 :0.5-6%, and/or Rn 2 O:0.5-6%, and/or Sb 2 O 3 :0-0.5%, and/or ZnO:0-5%, and/or Ta 2 O 5 :0-5%, and/or Al 2 O 3 ：0-5％。
6. The heavy lanthanum flint glass according to any one of claims 1 to 3, wherein the content of each component satisfies one or more of the following 5 cases:
1)B 2 O 3 /TiO 2 0.02-0.4;
2)BaO/B 2 O 3 is 3.6 to 64;
3)(La 2 O 3 +TiO 2 +ZrO 2 )/SiO 2 1.2-5;
4)(SiO 2 +La 2 O 3 +ZrO 2 )/TiO 2 1.1-3.7;
5)(SiO 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) Is 3.15-20.
7. The heavy lanthanum flint glass according to any one of claims 1 to 3, wherein: siO 2 2 :18-23%, and/or Ln 2 O 3 :16-18%, and/or La 2 O 3 :15-18%, and/or TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 :22-31%, and/or RO:23-30%, and/or ZrO 2 :2-6%, and/or B 2 O 3 :1-4%, and/or Rn 2 O:1-5%, and/or Sb 2 O 3 :0-0.2%, and/or ZnO:0-3%, and/or Ta-free 2 O 5 And/or does not contain Al 2 O 3 。
8. The heavy lanthanum flint glass according to any one of claims 1 to 3, wherein the content of each component satisfies one or more of the following 5 conditions:
1)B 2 O 3 /TiO 2 0.02-0.23;
2)BaO/B 2 O 3 is 5 to 30;
3)(La 2 O 3 +TiO 2 +ZrO 2 )/SiO 2 1.5 to 4;
4)(SiO 2 +La 2 O 3 +ZrO 2 )/TiO 2 1.2-2.0;
5)(SiO 2 +TiO 2 )/(B 2 O 3 +Nb 2 O 5 ) Is 3.36-12.00.
9. The heavy lanthanum flint glass according to any one of claims 1 to 3, wherein: tiO 2 2 :10-30%, and/or Nb 2 O 5 ：0.5-10％。
10. The heavy lanthanum flint glass of claim 9, wherein: tiO 2 2 :15-25%, and/or Nb 2 O 5 ：2-8％。
11. The heavy lanthanum flint glass of claim 10, wherein: tiO 2 2 :19-24%, and/or Nb 2 O 5 ：3-7％。
12. The heavy lanthanum flint glass according to any one of claims 1 to 3, wherein: la 2 O 3 :15-25%, and/or BaO:20-35%, and/or Na 2 O：0-8％。
13. The heavy lanthanum flint glass of claim 12, wherein: la 2 O 3 :15-22%, and/or BaO:22-32%, and/or Na 2 O：0.5-6％。
14. The heavy lanthanum flint glass of claim 13, wherein: la 2 O 3 :15-18%, and/or BaO:23-30%, and/or Na 2 O：1-5％。
15. Heavy lanthanum flint glass according to any one of claims 1 to 3, characterized in that λ of the glass 70 Is 450nm or less; lambda [ alpha ] 5 Is 390nm or less; the density (rho) of the glass is 4.5g/cm 3 The following; the upper limit temperature of crystallization of the glass is below 1200 ℃; the temperature coefficient of refractive index of the glass is 2.4 multiplied by 10 -6 Below/° c.
16. The heavy lanthanum flint glass of claim 15, wherein: lambda of the glass 70 Is 44Less than 0 nm;
λ 5 is 385nm or less; the density (rho) of the glass is 4.3g/cm 3 The following; the upper limit crystallization temperature of the glass is 1180 ℃ or lower; the temperature coefficient of refractive index of the glass is 2.3 x 10 -6 Below/° c.
17. The heavy lanthanum flint glass of claim 16, wherein: lambda of the glass 70 Is 430nm or less; lambda [ alpha ] 5 Is 380nm or less; the density (rho) of the glass is 4.25g/cm 3 The following.
18. Heavy lanthanum flint glass according to any one of claims 1 to 3, wherein the glass has a refractive index (nd) of 1.86 to 1.92; abbe number (vd) is 25-30.
19. The heavy lanthanum flint glass of claim 18, wherein: the glass has a refractive index (nd) of 1.86 to 1.91; abbe number (vd) is 25-29.
20. The heavy lanthanum flint glass of claim 19, wherein: the glass has a refractive index (nd) of 1.87 to 1.90; abbe number (vd) is 26-29.
21. Heavy lanthanum flint glass according to any of claims 1 to 3, characterised in that the glass has a transition temperature (T) g ) Below 720 ℃; stability of the glass to water action (D) W ) Is more than 2 types; stability against acid action (D) A ) Is more than 2 types.
22. The heavy lanthanum flint glass of claim 21, wherein: transition temperature (T) of the glass g ) Below 710 ℃; stability of the glass to water action (D) W ) Is of type 1; stability against acid action (D) A ) Is type 1.
23. The heavy lanthanum flint glass of claim 22Glass, its characterized in that: transition temperature (T) of the glass g ) At a temperature of 705 ℃ or lower.
24. A glass preform made from heavy lanthanum flint glass as recited in any of claims 1 to 23.
25. An optical element made from heavy lanthanum flint glass as recited in any one of claims 1 to 23, or from a glass preform as recited in claim 24.
26. An optical device made using the optical element of claim 25.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811493174.0A CN109502964B (en) | 2018-12-07 | 2018-12-07 | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof |
| JP2021532249A JP7311603B2 (en) | 2018-12-07 | 2019-11-21 | Heavy lanthanum flint glass, its preforms, optical elements, and optical instruments |
| PCT/CN2019/119809 WO2020114255A1 (en) | 2018-12-07 | 2019-11-21 | Heavy lanthanum flint glass, preform thereof, optical element and optical instrument |
| JP2023111446A JP2023134579A (en) | 2018-12-07 | 2023-07-06 | Heavy lanthanum flint glass, preform thereof, optical element and optical instrument |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811493174.0A CN109502964B (en) | 2018-12-07 | 2018-12-07 | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109502964A CN109502964A (en) | 2019-03-22 |
| CN109502964B true CN109502964B (en) | 2023-03-28 |
Family
ID=65753032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811493174.0A Active CN109502964B (en) | 2018-12-07 | 2018-12-07 | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof |
Country Status (3)
| Country | Link |
|---|---|
| JP (2) | JP7311603B2 (en) |
| CN (1) | CN109502964B (en) |
| WO (1) | WO2020114255A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109502964B (en) * | 2018-12-07 | 2023-03-28 | 成都光明光电股份有限公司 | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof |
| US11787729B2 (en) | 2020-05-18 | 2023-10-17 | Corning Incorporated | Glass compositions with high refractive indexes and low densities |
| WO2023183141A1 (en) | 2022-03-25 | 2023-09-28 | Corning Incorporated | Optical glasses containing bismuth oxide |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5950048A (en) * | 1982-09-16 | 1984-03-22 | Ohara Inc | Optical glass |
| BR8605356A (en) * | 1985-11-29 | 1987-08-04 | Corning Glass Works | GLASS FOR OPTICAL AND / OR OPHTHALMIC APPLICATIONS |
| DE10122263C2 (en) * | 2001-05-08 | 2003-04-03 | Schott Glas | Optical glasses and their use |
| JP2007008761A (en) * | 2005-06-30 | 2007-01-18 | Konica Minolta Opto Inc | Optical glass and optical element |
| JP2009203155A (en) * | 2008-01-31 | 2009-09-10 | Ohara Inc | Optical glass |
| US9718106B2 (en) | 2013-09-25 | 2017-08-01 | Hitachi Metals, Ltd. | Centrifugally cast, hot-rolling composite roll |
| CN104944767B (en) * | 2014-03-26 | 2017-11-14 | 成都光明光电股份有限公司 | High-refractive and high-dispersive optical glass |
| JP2016108216A (en) * | 2014-11-26 | 2016-06-20 | セントラル硝子株式会社 | Fluorophor dispersion glass |
| JP7545192B2 (en) | 2016-10-03 | 2024-09-04 | 株式会社オハラ | Optical glass, preforms and optical elements |
| JP7076192B2 (en) * | 2016-11-30 | 2022-05-27 | 株式会社オハラ | Optical glass, preform materials and optical elements |
| CN110128007B (en) * | 2017-07-03 | 2022-07-15 | 成都光明光电股份有限公司 | Heavy lanthanum flint optical glass |
| CN117105524A (en) * | 2018-03-27 | 2023-11-24 | 成都光明光电股份有限公司 | Optical glass |
| CN109502964B (en) * | 2018-12-07 | 2023-03-28 | 成都光明光电股份有限公司 | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof |
-
2018
- 2018-12-07 CN CN201811493174.0A patent/CN109502964B/en active Active
-
2019
- 2019-11-21 WO PCT/CN2019/119809 patent/WO2020114255A1/en active Application Filing
- 2019-11-21 JP JP2021532249A patent/JP7311603B2/en active Active
-
2023
- 2023-07-06 JP JP2023111446A patent/JP2023134579A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN109502964A (en) | 2019-03-22 |
| JP7311603B2 (en) | 2023-07-19 |
| JP2022510707A (en) | 2022-01-27 |
| WO2020114255A1 (en) | 2020-06-11 |
| JP2023134579A (en) | 2023-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109721241B (en) | Optical glass, glass preform, optical element and optical instrument | |
| CN109264989B (en) | Optical glass, preform thereof, optical element and optical instrument | |
| CN109437556B (en) | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof | |
| CN113024107B (en) | High-refraction high-dispersion optical glass and optical element | |
| TWI779744B (en) | Optical glass, glass preform and optical element | |
| CN113292242B (en) | Special dispersion optical glass | |
| CN110255893B (en) | Optical glass, glass preform, optical element and optical instrument | |
| CN109081578B (en) | Optical glass, preform thereof, optical element and optical instrument | |
| CN113264675B (en) | Optical glass, optical element and optical instrument | |
| CN109650717B (en) | Optical glass | |
| CN110128005B (en) | Optical glass | |
| CN111960665B (en) | Optical glass | |
| CN109987835B (en) | Optical glass, glass preform, optical element and optical instrument | |
| CN109502964B (en) | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof | |
| CN113582537B (en) | High-refraction high-dispersion optical glass | |
| CN110590154A (en) | Optical glass | |
| CN109626815B (en) | Optical glass, glass preform, optical element and optical instrument | |
| CN109721240B (en) | Optical glass, glass preform, optical element and optical instrument | |
| CN111285602B (en) | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof | |
| CN115448591A (en) | Optical glass, optical element and optical instrument | |
| CN109851217B (en) | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof | |
| CN111285601B (en) | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof | |
| CN112159098A (en) | Optical glass, optical element and optical instrument | |
| CN115028353B (en) | Optical glass with negative anomalous dispersion | |
| WO2024041276A1 (en) | Optical glass, glass preform, optical element and optical instrument |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |