CN115974406A - A kind of optical glass, glass preform and optical element - Google Patents
A kind of optical glass, glass preform and optical element Download PDFInfo
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Abstract
本发明公开了一种光学玻璃、玻璃预制件及光学元件，其组分含有WO3，和La2O3、Bi2O3中的至少一种，摩尔百分比为：WO3：60～85％，La2O3：0～25％，Bi2O3：0～40％；或组分含有WO3、La2O3和ZnO，摩尔百分比为：WO3：50～85％，La2O3：5～25％，ZnO：≤40％；组分摩尔百分比之和为百分之百。所述光学玻璃在不含有SiO2、B2O3、P2O5网络形成体的前提下，能够获得较低的光学玻璃的玻璃化转变温度和较高的折射率，且达到模压成形的要求。
The invention discloses an optical glass, a glass preform and an optical element, the components of which contain WO 3 , and at least one of La 2 O 3 and Bi 2 O 3 , and the molar percentage is: WO 3 : 60-85% , La 2 O 3 : 0-25%, Bi 2 O 3 : 0-40%; or the component contains WO 3 , La 2 O 3 and ZnO, the molar percentage is: WO 3 : 50-85%, La 2 O 3 : 5-25%, ZnO: ≤40%; the sum of the mole percentages of the components is 100%. On the premise that the optical glass does not contain SiO 2 , B 2 O 3 , or P 2 O 5 network formers, it can obtain a lower glass transition temperature and a higher refractive index of the optical glass, and can achieve a molded Require.
Description
Technical Field
The invention relates to the technical field of optical glass, in particular to optical glass, a glass prefabricated member and an optical element.
Background
The aspheric glass lens is widely applied to equipment and devices such as vehicle-mounted lenses, security lenses, mobile phone lenses, projectors and the like, the traditional cold machining method is not suitable for the mass production of the aspheric lens, and the high-efficiency mass production of the aspheric lens can be realized by adopting a precision compression molding method. The lens made of the high-refraction optical glass can obtain a larger visual angle under a smaller volume, is used for manufacturing a small-size lens, and is very important for the development of portable electronic equipment. The glass has high refractive index and low glass transition temperature, and is an important development direction of the molded glass.
Chinese patent document CN1896022A discloses a high-refractive-index, high-dispersion optical glass having a refractive index of not less than 2.000 and an abbe number of not more than 27, but the glass has a high transition temperature, which is not favorable for press molding. Chinese patent document CN113024107A discloses a new compound d Is more than 1.95, and has Abbe number v d 25 or less, a transition temperature Tg of 520 ℃ or less, and a large amount of Bi contained therein 2 O 3 With higher costs, containing P 2 O 5 Volatility causes the components to shift. In addition, siO is included 2 、B 2 O 3 、P 2 O 5 Glasses made of network formers reduce the refractive index and are clearly disadvantageous for the production of high refractive lenses.
Based on the above, there is a need to provide an optical glass composition with high refractive index and low glass transition temperature, which satisfies the performance of mold pressing glass, and promotes the preparation of glass preform and the application of optical element.
Disclosure of Invention
The object of the present invention is to provide an optical glass, a glass preform and an optical element which do not contain SiO 2 、B 2 O 3 、P 2 O 5 On the premise of a network forming body, the requirements that the glass transition temperature and the refractive index of the optical glass reach the die forming are met.
In view of the above, the technical scheme of the invention is as follows:
an optical glass comprises WO 3 And La 2 O 3 、Bi 2 O 3 At least one of; the mol percentage is as follows: WO 3 ：60～85％，La 2 O 3 ：0～25％，Bi 2 O 3 :0 to 40 percent; the sum of the mole percentages of the components is one hundred percent.
Further, in the composition, when WO is contained 3 、La 2 O 3 When the component also contains ZrO 2 ，Al 2 O 3 ，Nb 2 O 5 At least one of; when only WO is contained 3 、Bi 2 O 3 When the component also contains ZrO 2 ，Al 2 O 3 ，ZnO，Nb 2 O 5 At least one of; the mol percentage is as follows: zrO (ZrO) 2 ：≤10％，Al 2 O 3 ：≤20％，ZnO：≤20％，Nb 2 O 5 : less than or equal to 15 percent; the sum of the mole percentages of the components is one hundred percent.
Preferably, the components have the following molar ratios: WO 3 ：65～80％，La 2 O 3 ：5～20％，Bi 2 O 3 ：10～30％，ZrO 2 ：≤6％，Al 2 O 3 ：≤8％，ZnO：≤10％；Nb 2 O 5 ：≤10％。
The present invention also provides another optical glass whose composition comprises WO 3 、La 2 O 3 And ZnO, the mole percentage is: WO 3 ：50～85％，La 2 O 3 ：5～25％，ZnO: less than or equal to 40 percent; the sum of the mole percentages of the components is one hundred percent.
Further, the component also contains ZrO 2 ，Bi 2 O 3 ，Al 2 O 3 ，Nb 2 O 5 At least one of the following components in percentage by mole: zrO (zirconium oxide) 2 ：≤10％，Bi 2 O 3 ：≤20％，Al 2 O 3 ：≤20％，Nb 2 O 5 : less than or equal to 15 percent; the sum of the mole percentages of the components is one hundred percent.
Preferably, the molar ratio of each component is: WO 3 ：60～75％；La 2 O 3 ：7～20％；ZnO：10～30％；ZrO 2 ：≤10％；Bi 2 O 3 ：≤10％；Al 2 O 3 ：≤10％；Nb 2 O 5 ：≤10％。
The invention also aims to provide a glass prefabricated member which is made of the optical glass.
Further, the glass preform has a glass transition temperature Tg of less than 600 ℃, preferably less than 550 ℃, more preferably less than 500 ℃; the refractive index is in the range of 1.9 to 2.31, preferably 2.0 to 2.31, more preferably 2.2 to 2.31.
Furthermore, the Abbe number is 15-25, the light transmission range is 350-6000 nm, and the internal transmittance of the 2mm glass is more than 98%.
The invention also provides a preparation method of the glass preform, which comprises the following steps:
s1, grinding the raw materials of all the components into powder in a ball way, and pressing the powder into tablets;
s2, sintering the sheet at 800-1200 ℃ for 6-12 h;
s3, melting glass by using a suspension melting furnace, heating to melt the flaky raw materials, keeping the flaky raw materials in a suspension state under the action of airflow, homogenizing the melt, and cooling to obtain the glass prefabricated member.
Further, in step S3, the heating homogenization temperature is 800-1500 ℃, and the heat preservation homogenization time is 0.2-2 min.
Further, in step S3, the gas flow is oxygen or compressed air, and the flow rate is 1000 to 6000sccm.
It is still another object of the present invention to provide an optical element made of the above optical glass or the above glass preform.
It is still another object of the present invention to provide a method for manufacturing an optical element, in which the above glass preform is heated and precision press-molded using a press-molding die.
Compared with the prior art, the beneficial effects of the invention include but are not limited to:
1. the optical glass provided by the invention does not contain SiO 2 、B 2 O 3 、P 2 O 5 On the premise of network formation, the use of a catalyst containing WO 3 The glass system can obtain lower glass transition temperature and higher refractive index of the optical glass and meet the requirement of mould pressing forming.
2. The lowest glass transition temperature of the optical glass or the glass prefabricated member provided by the invention can be below 500 ℃, the refractive index can reach 2.2-2.31, and the optical glass or the glass prefabricated member has good prospect when being applied to preparing optical elements by die forming.
3. The preparation method of the glass prefabricated member provided by the invention ensures that the glass is not contacted with a container in the forming process by using the gas suspension melting technology, thereby overcoming the defect that the components do not contain SiO 2 、B 2 O 3 、P 2 O 5 The glass forming is difficult when the network forming body is formed.
Drawings
FIG. 1 shows that the component of example 1 of the present invention is 10La 2 O 3 -67.5WO 3 -22.5 refractive index dispersion map of a colorless nearly spherical molded glass of ZnO.
FIG. 2 shows 5La as the component in example 2 of the present invention 2 O 3 -70WO 3 -25Bi 2 O 3 Refractive index dispersion map of colorless nearly spherical molded glass.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The components and their contents in the optical glass of the present invention are explained, and in the following, the colorless nearly spherical shaped press glass of the present invention may be simply referred to as glass. In the embodiment of the present invention, the contents and the total contents of the respective components are all expressed in terms of mole percent (mol%), that is, the contents and the total contents of the respective components are expressed in terms of mole percent with respect to the total amount of the glass substance converted into the composition of oxides, if not specifically stated. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the optical glass composition component of the present invention are decomposed and converted to oxides when melted, the total amount of the oxides is 100%.
In a first embodiment, an optical glass is provided, the composition of which comprises WO 3 And La 2 O 3 、Bi 2 O 3 At least one of; the mol percentage is as follows: WO 3 ：60～85％，La 2 O 3 ：0～25％，Bi 2 O 3 :0 to 40 percent; the sum of the mole percentages of the components is one hundred percent. The glass transition temperature Tg is lower than 600 deg.C, and its refractive index range is 1.9-2.31.
As a preference of the first embodiment, when the component is WO 3 、La 2 O 3 、Bi 2 O 3 In the above molar ratio range, the glass transition temperature Tg is less than 550 ℃ and the refractive index is in the range of 2.15 to 2.31.
In a second embodiment, an optical glass is provided, the composition of which comprises WO 3 And La 2 O 3 、Bi 2 O 3 And other components; in particular, the component is WO 3 、La 2 O 3 And ZrO 2 、Al 2 O 3 、Nb 2 O 5 At least one of; or, its component is WO 3 、La 2 O、Bi 2 O 3， And ZrO 2 、Al 2 O 3 、Nb 2 O 5 At least one of; or, its component is WO 3 、Bi 2 O 3 And ZrO 2 、Al 2 O 3 、ZnO、Nb 2 O 5 At least one of; the mol percentage is as follows: zrO (ZrO) 2 ：≤10％，Al 2 O 3 ：≤20％，ZnO：≤20％，Nb 2 O 5 : less than or equal to 15 percent; the sum of the mole percentages of the components is one hundred percent. The glass transition temperature Tg is lower than 550 ℃, and the refractive index range is 2.0-2.31.
In a second preferred embodiment, the optical glass composition comprises the following components in a molar ratio: WO 3 ：65～80％，La 2 O 3 ：5～20％，Bi 2 O 3 ：10～30％，ZrO 2 ：≤6％，Al 2 O 3 ：≤8％，ZnO：≤10％；Nb 2 O 5 : less than or equal to 10 percent. The glass transition temperature Tg is lower than 500 deg.C, and the refractive index range is 2.2-2.31.
In a third embodiment, another optical glass is provided, the composition of which contains WO 3 、La 2 O 3 And ZnO, the mole percentage is: WO 3 ：50～85％，La 2 O 3 :5 to 25%, znO: less than or equal to 40 percent; the sum of the mole percentages of the components is one hundred percent. The glass transition temperature Tg is lower than 550 ℃, and the refractive index range is 1.9-2.15.
In a fourth embodiment, another optical glass is provided, which has the composition WO 3 、La 2 O 3 、Bi 2 O 3 And ZnO, the mole percentage is: WO 3 ：50～85％，La 2 O 3 ：5～25％，Bi 2 O 3 : less than or equal to 20%, znO: less than or equal to 40 percent, the glass transition temperature Tg of the copolymer is less than 550 ℃ within the molar ratio range, the refractive index is in the range of 1.9 to 2.31.
In a fifth embodiment, another optical glass is provided, which has the composition WO 3 、La 2 O 3 ZnO and ZrO 2 ，Al 2 O 3 ，Nb 2 O 5 At least one of the following components in percentage by mole: WO 3 ：50～85％，La 2 O 3 ：5～25％，ZnO：≤40％；ZrO 2 ：≤10％，Al 2 O 3 ：≤20％，Nb 2 O 5 : less than or equal to 15 percent; the sum of the mole percentages of the components is one hundred percent. The glass transition temperature Tg is lower than 550 ℃, and the refractive index range is 1.9-2.15.
As a preference of the fifth embodiment, the optical glass comprises the following components in a molar ratio: WO 3 ：60～75％；La 2 O 3 ：7～20％；ZnO：10～30％；ZrO 2 ：≤10％；Al 2 O 3 ：≤10％；Nb 2 O 5 : less than or equal to 10 percent. The glass transition temperature Tg is lower than 500 deg.C, and the refractive index range is 1.9-2.15.
SiO 2 、B 2 O 3 And P 2 O 5 Generally, an optical glass network former, but the addition thereof limits the increase in the refractive index of the glass and is disadvantageous in infrared transmission, and therefore this component is not used in the above examples.
La 2 O 3 Is a component necessary for improving the stability of the glass and the refractive index, but too much causes the glass to be particularly liable to devitrify, so that La 2 O 3 The content is 0 to 25%, preferably 5 to 20%.
ZrO 2 In order to increase the refractive index component, but to raise the glass transition temperature too much, zrO in the present invention 2 The content is 0 to 10%, preferably 0 to 6%.
WO 3 For the high refractive index component and the simultaneous lowering of the glass transition temperature, the above examples were conducted by containing 50% or more of WO 3 To obtain the above effects, WO of preferably 60%, more preferably 65%, or more is preferable 3 Cause a decrease in thermal stability and a decrease in devitrification resistance, WO 3 The upper limit of the content is 85%, preferably 80%, more preferably 75%.
Bi 2 O 3 Can improve the refractive index of the glass, reduce the transition temperature and does not contain Bi 2 O 3 The glass can also be shaped, in order to obtain a reduced glass transition temperature, bi 2 O 3 The content is preferably 10% or more. However, bi 2 O 3 When the content is high, the light transmittance of the glass is lowered, and the abrasion and chemical stability are deteriorated, and Bi in the above examples 2 O 3 The upper limit of the content is 40%, preferably 30%.
Al 2 O 3 The compactness of the internal structure of the glass can be improved, and the ultraviolet transmittance and the chemical stability of the glass are improved, but if the content of the ultraviolet transmittance and the chemical stability exceeds 20 percent, the internal quality of the glass is deteriorated, and the melting temperature is increased. Thus, al 2 O 3 The upper limit of the content of (b) is 20%, preferably 10%, more preferably 8%.
ZnO can adjust the refractive index of the glass, reduce the high-temperature viscosity and the glass-transition temperature of the glass, and lead the glass to be melted at lower temperature. On the other hand, if the content of ZnO is too high, the refractive index of the glass decreases, and the devitrification resistance is deteriorated. Accordingly, the ZnO content is 0 to 40%, preferably 10 to 30%, more preferably 10 to 20%.
Nb 2 O 5 Can improve the refractive index, light transmittance and devitrification resistance of the glass, but Nb 2 O 5 The addition of (b) increases the glass transition temperature, so that the upper limit of the content thereof is limited to 20%, preferably 10%.
In the two optical glass embodiments, the Abbe number is 15-25, the light transmission range is 350-6000 nm, and the internal transmittance of the 2mm glass is more than 98%.
In a third embodiment, a method for producing an optical glass preform is provided, comprising the steps of:
1. vitreous body preparation
Weighing powder raw materials according to a stoichiometric ratio, adding pure water, adding or not adding a binder, uniformly grinding in a ball mill for 6-12 h at a rotation speed of 150-300 r/min, wherein the binder is PVA aqueous solution generally, the concentration of PVA is 2-5%, and the adding amount of the PVA aqueous solution is 1-5% of the weight of the powder.
After grinding, the ball material is separated, the slurry is dried in a drying oven at 60-150 ℃ for 5-12 h, and the water content of the powder after drying is preferably below 30% in order to achieve better fluidity according to the water content of the slurry.
And (3) granulating the powder, and pressing the granulated powder into tablets by using a tablet press, wherein the diameter of the tablets is 3-10 mm, the tablets pressed by overlarge pressure are easy to delaminate, and the tablets pressed by undersize pressure are not easy to crush due to insufficient density. The web weight deviation is controlled to be 2% or less, preferably 1% or less, depending on the optical element requirements.
Presintering the pressed sheet in a muffle furnace, heating at the speed of 10 ℃/min, preserving heat at the temperature of 800-1200 ℃ for 6-12 h, and then cooling with the furnace.
The flaky raw material is placed in a suspension smelting furnace, the suspension gas is oxygen and compressed air, preferably oxygen, the oxidation atmosphere is maintained, and the coloring caused by valence change of metal ions is prevented. Heating a sample from the top by laser to melt the sample into a spherical shape, wherein the power of a single laser is 20-100W, the heat preservation temperature is 800-1500 ℃, the heat preservation temperature is slightly higher than the melting temperature of the sample, the temperature is too low, the melt is slowly homogenized, and the melt below is easy to nucleate and solidify; the temperature is too high, the surface tension of the melt is weak, the melt is easy to crack under the airflow, and the formed glass has poor sphericity. The method comprises the steps of regulating and controlling temperature rise and temperature reduction of a sample, discharging internal bubbles by utilizing the change of melt viscosity, regulating the size of airflow to enable the sample to be stably suspended, controlling the flow of the airflow to be 1000-6000 sccm, regulating according to the weight of glass, keeping the temperature for 0.2-2 min in a stable state to enable the melt to be homogenized, turning off a laser, rapidly cooling the sample, and rapidly solidifying to form a colorless glass sphere with the diameter of 1-10 mm.
2. Polishing of glass bodies
Packaging the prepared glass ball in epoxy resin for polishing, and specifically operating as follows:
(1) Placing a glass ball with proper size in a rubber mould, preparing epoxy resin and a curing agent, and pouring the epoxy resin and the curing agent into the mould to cover the glass ball properly. And taking out after the resin is hardened.
(2) Polishing a test surface: and taking out the packaged sample, polishing the packaged sample on a polishing machine, performing coarse grinding by using 400, 600 and 1000-mesh sand paper, and finally spraying 0.1-0.5 micron diamond polishing solution or cerium oxide polishing solution on flannelette for polishing, wherein the surface of the glass has no obvious scratch when observed under an optical microscope.
(3) Back treatment: the back side is coarsely ground to be parallel to the test surface without polishing glass and without requiring the resin surface to be smooth.
3. Characterization test
(1) Refractive index test
The refractive index of the glass is measured by an elliptical polarization tester, and the refractive index is obtained by analyzing the change of polarization states of incident light and reflected light on the surface of the glass and fitting the polarization states by a Cauchy formula. Due to the retro-reflection principle of the semi-spherical sample after polishing, the refracted light of the inner and lower cambered surfaces of the glass hardly influences the collected reflected light, and the test accuracy is improved. The test wavelength range is 300-1600nm, and the test angle is 55 degrees.
(2) Test of light transmittance
Polishing the back surface of the package body to an optical mirror surface as in the polishing operation, keeping the two surfaces parallel, and taking out a sample after polishing to obtain a polished thickness of 2mm, testing the visible-near infrared transmittance by using an ultraviolet-visible-near infrared spectrophotometer, and testing the middle-infrared transmittance by using a Fourier infrared spectrometer, wherein the testing range is from ultraviolet to infrared cutoff.
(3) Hardness test
The hardness of the glass sheet is measured by a microhardness tester, the load is 300g, and the average value is obtained by multiple tests in different areas.
The polishing process adopts resin to encapsulate and polish sample glass, so that the problems of small sample size and difficult clamping are solved; a plurality of samples with different components are packaged at one time, so that the sample processing efficiency is improved; the packaging block body is large in size, and the parallelism during two-side polishing is improved; the polished glass beads are hemispherical, and due to reflection of the inner wall of the glass cambered surface, interference of refracted light on a test result is reduced, and the test precision is improved.
The molar ratio of the ternary system glass forming region in the embodiment of the invention is obtained by multiple experiments, and the method in the invention is not limited to be used in other component materials. Although this step of characterization testing is shown in the above-mentioned optical glass preform production step, it is not essential to the production method of the colorless nearly spherical shaped press glass, but is merely for analyzing the results of the method.
The above embodiments provide optical glasses that do not contain SiO 2 、B 2 O 3 、P 2 O 5 The network forms bodies because these three components reduce the refractive index of the glass. On the other hand, the glass forming ability is reduced without using the network former, and the optical glass preform is produced by using the aerosol fusion technique without contacting the container during the glass forming process, thereby overcoming the problem of difficulty in glass forming. Compared with other prior art without network forming body, the glass has high refractive index, simultaneously has low glass transition temperature which is lower than 600 ℃, and meets the requirement of compression molding application. More preferably, the glass transition temperature of the optical glass prefabricated member can be lower than 500 ℃ on the basis of keeping high refractive index, and the optical glass prefabricated member is obviously superior to the existing glass and has good commercial application prospect.
In the optical glass components described in the above examples, lanthanum oxide can increase the refractive index of the glass and improve the devitrification ability of the glass, but can increase the glass transition temperature, tungsten oxide, bismuth oxide, and zinc oxide have higher refractive indices and can lower the glass transition temperature, and zirconium oxide, aluminum oxide, and niobium oxide can increase the refractive index, but excessive addition can increase the glass transition temperature. The cooling of the glass melt to form glass needs to overcome internal crystallization, the rapid cooling and the avoidance of container contact nucleation are main ways, the vitrification or crystallization in the cooling process of the glass melt is also a complex physical process, the influence among the components of the glass is complex, the stability of the interior is often damaged by excessive components, the melt can cross a crystallization area to form the glass only by proper components, the proper components can be obtained by a large number of experiments, and the proper components are not obtained by simple derivation of the existing system.
In a fourth embodiment, an optical element is provided, in which the optical glass preform described above is used, or a means of compression molding such as hot press molding and precision press molding is used to manufacture various lenses, especially aspheric lenses, and vehicle-mounted lenses, security lenses, mobile phone lenses, projectors and the like which are manufactured by using aspheric lenses.
The compositions of the examples of the optical glass portions described above are shown in tables 1 to 4 (Table 4 includes tables 4-1, 4-2 and 4-3).
Table 1: the component contains WO 3 And La 2 O 3 、Bi 2 O 3 At least one of
Table 2: the component contains WO 3 、La 2 O 3 And further contains Bi 2 O 3 ，ZrO 2 ，Al 2 O 3 ，Nb 2 O 5 At least one of; containing WO 3 、Bi 2 O 3 And also contains ZrO 2 ，Al 2 O 3 ，ZnO，Nb 2 O 5 At least one of
Table 3: WO 3 、La 2 O 3 And ZnO
TABLE 4-1: the component contains WO 3 、La 2 O 3 ZnO, and Bi 2 O 3 、ZrO 2 、Al 2 O 3 、Nb 2 O 5 At least one of
Tables 4-2: the component contains WO 3 、La 2 O 3 ZnO, and Bi 2 O 3 、ZrO 2 、Al 2 O 3 、Nb 2 O 5 At least one of
Tables 4 to 3: the component contains WO 3 、La 2 O 3 ZnO, and Bi 2 O 3 、ZrO 2 、Al 2 O 3 、Nb 2 O 5 At least one of
Because the melting temperatures of different components are different, the laser power during melting needs to be adjusted to completely melt the raw materials, the preparation methods of the glass preforms are basically the same except for the different laser powers, and the following preparation examples are specifically explained by selecting some of the above examples.
Preparation example 1:10La 2 O 3 -67.5WO 3 -22.5ZnO
The optical glass preform preparation process is as described above, and the raw material La is weighed according to the stoichiometric ratio 2 O 3 、WO 3 And putting ZnO in a ball mill, adding pure water and PVA solution, and ball-milling for 12 hours. Sieving the grinding balls to separate from the slurry, drying the slurry powder in a drying oven at 100 ℃, sieving and granulating the powder, keeping the granularity between 40 and 100 meshes, pressing the powder into a circular tablet with the diameter of 4mm by using an automatic tablet press, and controlling the weight deviation of the tablet to be below 2 percent according to the requirement of an optical element. And (3) putting the pressed tablets into a muffle furnace, sintering at 900 ℃, and preserving heat for 6 hours. Melting glass using the suspension laser heating furnace60mg of the glass is taken each time, the gas flow is controlled to be 1000sccm, the glass is completely melted and is in a suspension state, the laser power is adjusted, the temperature is controlled to be 1000 ℃, the heat preservation is carried out for 1min, the laser is turned off, and the glass is rapidly cooled to the room temperature under the gas flow, so that the colorless subsphaeroidal molded glass is prepared. The glass transition temperature is measured by taking 30-60 mg of glass, and the Tg is 489 ℃ as a test result. Polishing glass ball with diameter of 4mm or more into glass sheet with smooth both surfaces, and measuring transmittance and refractive index, as shown in FIG. 1, n at 587.6nm d 1.972, abbe number 21.6, and hardness 350X 10 under a 300g load 7 Pa. The light transmittance graph shows that the light transmission wavelength range is 370-6000nm.
Preparation example 2:5La 2 O 3 -70WO 3 -25Bi 2 O 3
The preparation process of the optical glass prefabricated member is as described above, and the raw material La is weighed according to the stoichiometric ratio 2 O 3 、WO 3 、Bi 2 O 3 Putting the mixture into a ball mill, adding pure water and PVA solution, and ball-milling for 10 hours. Sieving the grinding balls to separate from the slurry, drying the slurry powder in a drying oven at 80 ℃, sieving and granulating the powder, keeping the granularity between 40 and 100 meshes, pressing the powder into a circular tablet with the diameter of 4mm by using an automatic tablet press, and controlling the weight deviation of the tablet to be below 2 percent according to the requirement of an optical element. And (3) putting the pressed tablets into a muffle furnace, sintering at 800 ℃, and preserving heat for 8 hours. And (3) smelting glass by using a suspension laser heating furnace, controlling the gas flow to be 6000sccm each time by taking 600mg to ensure that the glass is completely molten and in a suspension state, regulating the laser power, controlling the temperature to be 900 ℃, keeping the temperature for 2min to homogenize the glass, closing the laser, and rapidly cooling the glass to room temperature under the gas flow to prepare the colorless nearly spherical molded glass. The glass transition temperature is measured by taking 30-60 mg of glass, and the Tg is 490 ℃ as a result. Polishing glass ball with diameter of 4mm or more into glass sheet with smooth both surfaces, and testing transmittance and refractive index, as shown in FIG. 2, at n of 587.6nm d 2.303, abbe number 18.5, and hardness 456X 10 under a load of 300g 7 Pa. The light transmittance graph shows that the light transmission wavelength range is 370-6000nm.
Preparation example 3:10La 2 O 3 -3ZrO 2 -60WO 3 -2Bi 2 O 3 -2Al 2 O 3 -20ZnO-3Nb 2 O 5
The preparation process of the optical glass prefabricated member is as described above, and the raw material La is weighed according to the stoichiometric ratio 2 O 3 、ZrO 2 、WO 3 、Bi 2 O 3 、Al 2 O 3 、ZnO、Nb 2 O 5 Putting the mixture into a ball mill, adding pure water and PVA solution, and ball-milling for 10 hours. Sieving the grinding balls to separate from the slurry, drying the slurry powder in a drying oven at 80 ℃, sieving and granulating the powder, keeping the granularity between 40 and 100 meshes, pressing the powder into a round tablet with the diameter of 4mm by using an automatic tablet press, and controlling the weight deviation of the tablet to be below 2 percent according to the requirement of an optical element. And (3) putting the pressed tablets into a muffle furnace, sintering at 1100 ℃, and preserving heat for 10 hours. And (2) smelting glass by using a suspension laser heating furnace, taking 300mg each time, controlling the gas flow at 4500sccm to enable the glass to be completely molten and in a suspension state, adjusting the laser power, controlling the temperature of 1400 ℃ to be kept for 0.5min to enable the glass to be homogenized, turning off the laser, and rapidly cooling to room temperature under the gas flow to prepare the colorless nearly spherical molded glass. The glass transition temperature is measured by taking 30-60 mg of glass, and the Tg is 564 ℃. Polishing glass ball with diameter of 4mm or more into glass sheet with smooth two surfaces, and testing transmittance and refractive index at 587.6nm d 1.992, an Abbe number of 23.1 and a hardness of 486X 10 under a load of 300g 7 Pa. The light transmittance curve shows the light transmission wavelength range of 370-6000nm.
Finally, it should be noted that, although the present invention has been described in detail by using the general description and the specific embodiments, on the basis of the present invention, the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (14)
1. An optical glass characterized in that its composition contains WO 3 And La 2 O 3 、Bi 2 O 3 At least one of (a); the mol percentage is as follows: WO 3 ：60～85％，La 2 O 3 ：0～25％，Bi 2 O 3 :0 to 40 percent; the sum of the mole percentages of the components is one hundred percent.
2. An optical glass according to claim 1, characterised in that it comprises, as constituents, WO 3 、La 2 O 3 When the component also contains ZrO 2 ，Al 2 O 3 ，Nb 2 O 5 At least one of; when only WO is contained 3 、Bi 2 O 3 When the component also contains ZrO 2 ，Al 2 O 3 ，ZnO，Nb 2 O 5 At least one of; the mol percentage is as follows: zrO (ZrO) 2 ：≤10％，Al 2 O 3 ：≤20％，ZnO：≤20％，Nb 2 O 5 : less than or equal to 15 percent; the sum of the mole percentages of the components is one hundred percent.
3. The optical glass according to claim 2, wherein the composition comprises the following components in a molar ratio: WO 3 ：65～80％，La 2 O 3 ：5～20％，Bi 2 O 3 ：10～30％，ZrO 2 ：≤6％，Al 2 O 3 ：≤8％，ZnO：≤10％；Nb 2 O 5 ：≤10％。
4. An optical glass characterized in that its composition contains WO 3 、La 2 O 3 And ZnO, the mole percentage is: WO 3 ：50～85％，La 2 O 3 :5 to 25%, znO: less than or equal to 40 percent; the sum of the mole percentages of the components is one hundred percent.
5. An optical glass according to claim 4, characterised in that its composition also contains ZrO 2 ，Bi 2 O 3 ，Al 2 O 3 ，Nb 2 O 5 At least one of the following components in percentage by mole: zrO (zirconium oxide) 2 ：≤10％，Bi 2 O 3 ：≤20％，Al 2 O 3 ：≤20％，Nb 2 O 5 : less than or equal to 15 percent; the sum of the mole percentages of the components is one hundred percent.
6. The optical glass according to claim 5, wherein the molar ratio of each component is: WO 3 ：60～75％；La 2 O 3 ：7～20％；ZnO：10～30％；ZrO 2 ：≤10％；Bi 2 O 3 ：≤10％；Al 2 O 3 ：≤10％；Nb 2 O 5 ：≤10％。
7. Glass preform, characterized in that it is made of an optical glass according to any one of claims 1 to 6.
8. The glass preform according to claim 7, characterized in that it has a glass transition temperature Tg lower than 600 ℃, preferably lower than 550 ℃, more preferably lower than 500 ℃; the refractive index is in the range of 1.9 to 2.31, preferably 2.0 to 2.31, more preferably 2.2 to 2.31.
9. A glass preform according to claim 7, wherein the Abbe number is from 15 to 25, the optical transmission range is from 350 to 6000nm, and the internal transmission of the 2mm glass is greater than 98%.
10. The method for producing a glass preform according to claim 7, comprising the steps of:
s1, grinding the raw materials of the components into powder in a ball-milling mode, and pressing the powder into tablets;
s2, sintering the sheet at 800-1200 ℃ for 6-12 h;
and S3, melting the glass by using a suspension smelting furnace, heating to melt the flaky raw materials, keeping the flaky raw materials in a suspension state under the action of airflow, homogenizing the melt, and cooling to obtain the glass prefabricated member.
11. The method according to claim 10, wherein the temperature of the heating and homogenizing in step S3 is 800 to 1500 ℃, and the temperature of the heating and homogenizing is maintained for 0.2 to 2min.
12. The method according to claim 10, wherein the gas flow in step S3 is oxygen or compressed air with a flow rate of 1000 to 6000sccm.
13. Optical element, characterized in that it is made of an optical glass according to any one of claims 1 to 6 or a glass preform according to any one of claims 7 to 9.
14. A method for manufacturing an optical element, characterized in that the glass preform according to any one of claims 7 to 9 is heated and precision press-molded using a press-molding die.
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