CN113511810B - High-refractive-index optical glass and preparation method thereof - Google Patents
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Abstract
The invention discloses high-refractive-index optical glass and a preparation method thereof. The high-refractive-index optical glass comprises a base glassGlass and anti-reflective coatings; the raw material of the base glass contains In-W composite nanoparticles; the In-W composite nanoparticles consist of WO (tungsten oxide) with the mass ratio of (0.5-0.7): 13And In2O3And pre-doping to obtain the product. Has the advantages that: using WO3And In2O3Pre-doping, inhibiting the corrosivity of the single metal oxide, reforming the light absorption band gap by utilizing the interaction of two metal dipoles, further enhancing the refractive index and the light transmittance of the optical glass, and reducing WO3And In2O3The corrosion resistance of the glass is further enhanced by the use of two metals; and use of Ce-Cu-TiO2The metal effect induces and generates high-refraction low-dispersion high-transmittance bismuth silicate crystals, and further enhances the performance and quality of the glass.
Description
Technical Field
The invention relates to the technical field of optical glass, in particular to high-refractive-index optical glass and a preparation method thereof.
Background
The optical glass is a glass material which takes refractive index, Abbe number and transmittance as main key technologies and transmits light rays in a refraction and reflection transmission mode. It is used for manufacturing lenses, prisms, mirrors, windows, etc., and is widely used in optical instruments such as cameras, microscopes, etc. Among them, the high refractive index and dispersion determine the basic properties of the optical glass. Currently studied, since the higher the refractive index is, the thinner and lighter the optical glass is, and the better the light transmittance is, the production of the optical glass having a higher refractive index is sought. However, in general, the refractive index is inversely proportional to the dispersion, and an increase in the refractive index causes an increase in the dispersion, which causes an image blur and thus affects the use. Therefore, it is required to produce a high-refractive, low-dispersion optical glass.
In the prior art, high refractive index, low dispersion optical glasses have generally achieved this requirement through the addition of lanthanide metal oxides. However, the lanthanide metal oxide limits the increase of the refractive index and is relatively expensive to manufacture. Thus, in the previously studied patent CN202110218396.7, tungsten oxide and La were mixed2O3、Y2O3、 In2O3The functions of high refraction and low dispersion are realized in cooperation. However, the tungsten oxide and the zinc oxide used in the patent have strong corrosiveness, so that the corrosion to equipment in the preparation process is increased; meanwhile, a specific antireflection coating is not disclosed, and properties such as refractive index are to be further improved. In addition, since the optical glass used in optical instruments generally uses acetone as a scrubbing solvent, acetone resistance is one of the properties required for the optical glass.
Therefore, in order to solve the above problems and further improve the refractive index of the optical glass, the antireflection property and acetone resistance of the optical glass are increased. A high-refraction optical glass and its preparing process are disclosed.
Disclosure of Invention
The present invention is directed to a high refractive index optical glass and a method for manufacturing the same, which solves the above problems of the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a high refractive index optical glass comprising a base glass and an antireflection coating; the raw material of the base glass contains In-W composite nanoparticles; the In-W composite nanoparticles consist of WO (tungsten oxide) with the mass ratio of (0.5-0.7): 13And In2O3And pre-doping to obtain the product.
Preferably, the raw materials of the base glass comprise a base material and a functional material; the base material comprises the following components: by weight: 22-30 parts of In-W composite nanoparticles; 12-18 parts of La2O3(ii) a 2-4 parts of Y2O3(ii) a 34 to 38 parts of B2O3(ii) a 8-10 parts of SiO2(ii) a 25 to 28 parts of Zn-Bi2O3(ii) a The functional material comprises the following components: 15-20 parts by weight of Ce-Cu-TiO2(ii) a 5-9 parts of Al2O3(ii) a 1 to 5 parts of Nb2O5(ii) a 1 to 5 parts of Ta2O5(ii) a 1-2 parts of Li2O。
Preferably, the Zn-Bi2O3Is Bi2O3Doped with Zn2+Obtained of Zn2+The doping amount is 8-10 wt%; the Ce-Cu-TiO2Is TiO2Middle doped Cu2+And Ce2+Obtained of Cu2+The doping amount is 10-15 wt% and Ce2+The doping amount is 15-18%.
Preferably, the preparation method of the high-refractive-index optical glass comprises the following steps:
step 1: (1) 22-30 parts of In-W composite nanoparticles; 12-18 parts of La2O3(ii) a 2-4 parts of Y2O3(ii) a 34 to 38 parts of B2O3(ii) a 8-10 parts of SiO2(ii) a 25 to 28 parts of Zn-Bi2O3Uniformly mixing to obtain a base material; 15-20 parts of Ce-Cu-TiO2(ii) a 5-9 parts of Al2O3(ii) a 1 to 5 parts of Nb2O5(ii) a 1 to 5 parts of Ta2O5(ii) a 1-2 parts of Li2Mixing the O uniformly to obtain a functional material; (2) heating and melting the base material at 1400-1500 ℃, preserving heat, and reducing the temperature to 680-720 ℃; adding functional materials for multiple times, heating to 1500-1600 ℃, preserving heat, clarifying, casting in a 670-680 ℃ mold, preserving heat for 4-5 hours, and slowly cooling at a cooling speed of 15-20 ℃; placing the glass substrate under gamma rays, setting the dose range to be 5-10 kGy, and irradiating to obtain base glass;
step 2: cleaning and drying the base glass, placing the base glass in a high-temperature high-pressure reaction kettle containing 2.5mol/L ammonium hydroxide solution, soaking for 4-6 hours at the temperature of 100-150 ℃, washing, and drying by nitrogen; spraying an antireflection solution on the surface of the substrate, and drying at 100-110 ℃; and transferring the glass to an atmospheric plasma discharge device, performing dielectric barrier discharge, setting an air gap to be 8mm, and processing for 3-5 minutes under the voltage of 30V to obtain the high-refractive-index optical glass.
Preferably, in step 1, the Zn-Bi2O3The preparation method comprises the following steps: ultrasonically dispersing bismuth nitrate in ethylene glycol, and dropwise adding a zinc nitrate solution; ultrasonic homogenization; placing the obtained solution in a microwave reactor, setting the power to 520W, reacting for 2-6 minutes, washing, filtering and drying; transferring the mixture to a high temperature furnace for reaction at 500-600 ℃ for 1-2 hours to obtain Zn-Bi2O3。
Preferably, in step 1, the Ce-Cu-TiO2The preparation method comprises the following steps: uniformly mixing tetrabutyl titanate, absolute ethyl alcohol and hydrofluoric acid, adding copper nitrate and cerium nitrate, continuously stirring for 3-4 hours to obtain a mixed solution, placing the mixed solution into a high-pressure reaction kettle, setting the temperature to be 160 ℃, carrying out hydrothermal reaction for 24 hours, washing, filtering and drying; calcining for 2-3 hours in a high-temperature transfer furnace at the temperature of 400-500 ℃ under the atmosphere of nitrogen to obtain Ce-Cu-TiO2。
Preferably, In step 1, the preparation method of the In-W composite nanoparticles comprises: dissolving ammonium metatungstate in deionized water, adding indium nitrate, stirring to form sol, adding polyvinyl alcohol solution, dropwise adding nitric acid, and homogenizing; freeze-drying; and transferring the mixture into a high-temperature box, and calcining the mixture for 4 hours at the temperature of 450-550 ℃ to obtain the In-W composite nanoparticles.
Preferably, the concentration of the polyvinyl alcohol solution is 4-6 wt%; the mass ratio of the polyvinyl alcohol solution to the sol is 4: 1.
Preferably, in step 2, the preparation method of the anti-reflection solution comprises: dissolving 3-aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane in ethanol; sequentially adding N-ethyl-N- (3-dimethylpropyl) carbodiimide, N-hydroxysuccinimide and stearic acid; adding silicon dioxide nano particles, and homogenizing to obtain an antireflection solution; wherein the mass ratio of the 3-aminopropyltriethoxysilane to the gamma-glycidoxypropyltrimethoxysilane is (3-4) to 1; the concentration of the silicon dioxide nano particles in the antireflection solution is 1-1.2 g/L; the stearic acid accounts for 30-35% of the total mass of the 3-aminopropyltriethoxysilane and the gamma-glycidoxypropyltrimethoxysilane.
In this technical solution, WO is still adopted3Instead of Gd2O3And is combined with In2O3、La2O3、Y2O3And matching to prepare the high-refractivity optical glass with low dispersion performance.
(1) Pre-doping tungsten In2O3In-W composite nano particles are obtained, and the composite nano particles contain a small amount of WO3And In2O3And a substantial portion of the In-W inter-doped nanoparticle oxide. In the process, WO is reduced3In direct dosage because of WO3And In2O3The instability of the oxide, the photo-generated electron-hole has strong oxidizing ability under illumination, and generates corrosivity with unstable metal ions, thereby damaging equipment and reducing the service life of the equipment. And pre-doping to improve the dipolar interaction between two metalsGood, light absorption band gap reforming, reduced WO3Further enhances the refractive index and light transmittance of the optical glass, and therefore, WO in the scheme3And In2O3The dosage of the two metals is reduced, and the corrosion resistance of the glass is further enhanced.
(2) Adding Zn-Bi2O3(ii) a Similarly, in order to reduce the corrosion to equipment in the preparation engineering, zinc oxide is not used in the scheme, and zinc ions are directly doped in Bi2O3In, Bi is enhanced2O3And the stability of the glass is enhanced while melting. In general, Bi2O3The glass density is increased in more times, and the melting process difficulty is increased; meanwhile, because zinc oxide is not added, crystallization phenomenon can be generated; but the two are doped in advance, optimized and complementary, and the existing difficulties are solved.
In addition, Zn-Bi2O3With SiO2Can generate high-refraction low-dispersion high-permeability bismuth silicate crystals, and further enhance the performance and quality of the glass. Of course, to promote the formation of this crystalline phase, Ce-Cu-TiO doped with copper ions is added2. Wherein the same doping of copper ions is to reduce the corrosion to the device. Meanwhile, the glass has optical stability due to the effect of Ce and Ti, and can realize reconstruction of a microstructure through network depolymerization under irradiation, recover structural defects and have radiation stability. And the effect between Cu and Ti reduces the activation energy in the system, induces the formation of bismuth silicate, accelerates the formation speed, has high growth efficiency and good integrity, thereby enhancing the permeability of visible light wave bands. In addition, the gamma ray treatment can convert bivalent copper into monovalent copper, promote the crosslinking of glass network, reduce the average grain size of glass and raise the strength and density of glass.
(3) The functions of other components are as follows: b is2O3And SiO2Is a network former in glass, and forms a firm silicon-oxygen tetrahedral three-dimensional network. Ta2O5The dispersion is reduced. Nb2O5The liquid phase temperature is reduced, and the crystallization is prevented; li2The bismuth silicate formed by the synergy of O lowers the Tg temperature of the glass.
(4) In general, optical instruments are wiped with acetone, and thus an antireflection coating is applied to the surface of the glass in order to reduce the reflectivity of the glass and the acetone resistance of the optical glass. And the antireflection property comes from the formation of nano-textures, and the light transmission path is increased.
The surface of the glass is treated by ammonium hydroxide at a certain temperature to form a uniform nano network, then nanopores formed by erosion of the surface of the glass are utilized to promote the diffusion of hydroxyl ions, and then the stearic acid is fixed on the aminated nano network by N-hydroxysuccinimide under the action of N-ethyl-N- (3-dimethylpropyl) carbodiimide. Enhancing the hydrophobicity. In addition, two siloxanes, namely 3-aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane, exist in the coating, and silicon dioxide connected with amino groups is fixed by chemical bonds under the induction of plasma under the action of atmospheric plasma; meanwhile, a large amount of ungrafted siloxane migrates to the top of the coating, so that the active oxygen promotes the crosslinking between the two types of siloxane and silicon dioxide, and the strength and the self-cleaning property of the coating are improved. So that the coating has acetone resistance.
Compared with the prior art, the invention has the following beneficial effects: (1) using WO3And In2O3Pre-doping, inhibiting the corrosivity of the single metal oxide, reforming the light absorption band gap by utilizing the interaction of two metal dipoles, further enhancing the refractive index and the light transmittance of the optical glass, and reducing WO3And In2O3The corrosion resistance of the glass is further enhanced by the use of two metals; (2) by using Zn-Bi2O3The medium zinc metal is doped, so that the fluxing property is improved, and the rewriting of the glass is enhanced; (3) using Ce-Cu-TiO2The metal effect induces and generates high-refraction low-dispersion high-transmittance bismuth silicate crystals, and further enhances the performance and quality of the glass. The gamma ray treatment is utilized to convert bivalent copper into monovalent copper, promote the crosslinking of the glass network and reduce the flatness in the glassThe grain size of the homogeneous crystal grains enhances the strength and density of the glass. (4) By utilizing the properties in the antireflection film, the antireflection property, the self-cleaning property and the acetone resistance of the optical glass are enhanced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1:
step 1: (1) ultrasonically dispersing bismuth nitrate in ethylene glycol, and dropwise adding a zinc nitrate solution; ultrasonic homogenization; placing the obtained solution in a microwave reactor, setting the power at 520W for reaction for 5 minutes, washing, filtering and drying; transferring the mixture to a high temperature furnace for setting, wherein the setting temperature is 550 ℃, and reacting for 1.5 hours to obtain Zn-Bi2O3. (2) Uniformly mixing tetrabutyl titanate, absolute ethyl alcohol and hydrofluoric acid, adding copper nitrate and cerium nitrate, continuously stirring for 3.5 hours to obtain a mixed solution, placing the mixed solution into a high-pressure reaction kettle, setting the temperature to be 160 ℃, carrying out hydrothermal reaction for 24 hours, washing, filtering and drying; calcining the mixture for 2.5 hours in a high-temperature transfer furnace at the temperature of 450 ℃ under the atmosphere of nitrogen to obtain the Ce-Cu-TiO2. (3) Dissolving ammonium metatungstate in deionized water, adding indium nitrate, stirring to form sol, adding polyvinyl alcohol solution, dropwise adding nitric acid, and homogenizing; freeze-drying; and transferring the mixture into a high-temperature box, and calcining the mixture for 4 hours at 500 ℃ to obtain the In-W composite nanoparticles.
Step 2: (1) 28 parts of In-W composite nanoparticles; 16 parts of La2O3(ii) a 3 parts of Y2O3(ii) a 35 parts of B2O3(ii) a 9 parts of SiO2(ii) a 26 parts of Zn-Bi2O3Uniformly mixing to obtain a base material; 18 parts of Ce-Cu-TiO2(ii) a 6 parts of Al2O3(ii) a 2 parts of Nb2O5(ii) a 2 parts of Ta2O5(ii) a 2 parts of Li2Mixing the O uniformly to obtain a functional material; (2)heating and melting the base material at 1450 ℃, preserving heat, and reducing the temperature to 700 ℃; adding functional materials for multiple times, heating to 1550 ℃, preserving heat, clarifying, casting in a 675 ℃ mould, preserving heat for 4 hours, and setting the cooling speed to be 18 ℃ for slow cooling; placing the glass substrate under gamma rays, setting the dose range to be 8 kGy, and irradiating to obtain base glass;
and step 3: (1) cleaning and drying the base glass, placing the base glass in a high-temperature high-pressure reaction kettle containing 2.5mol/L ammonium hydroxide solution, soaking for 4 hours at the set temperature of 150 ℃, washing, and drying by nitrogen; (2) dissolving 3-aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane in ethanol; sequentially adding N-ethyl-N- (3-dimethylpropyl) carbodiimide, N-hydroxysuccinimide and stearic acid; adding silicon dioxide nano particles, and homogenizing to obtain an antireflection solution; (3) spraying an antireflection solution on the surface of the substrate, and drying at 105 ℃; transferring the glass to an atmospheric plasma discharge device, performing dielectric barrier discharge, setting an air gap to be 8mm, and processing for 4 minutes under the voltage of 30V to obtain the high-refractive-index optical glass.
In the scheme, the In-W composite nanoparticles are prepared from the following components In a mass ratio of 0.6: 1 WO3And In2O3And pre-doping to obtain the product. The Zn-Bi2O3Is Bi2O3Doped with Zn2+Thus, the doping amount is 9 wt%; the Ce-Cu-TiO2Is TiO2Middle doped Cu2+And Ce2+Obtained of Cu2+The doping amount is 12wt% and Ce2+The doping amount is 16%. The concentration of the polyvinyl alcohol solution is 3 wt%; the mass ratio of the polyvinyl alcohol solution to the sol is 4: 1. The mass ratio of the 3-aminopropyltriethoxysilane to the gamma-glycidoxypropyltrimethoxysilane is 3.5: 1; the concentration of the silicon dioxide nano particles in the antireflection solution is 1.2 g/L; the stearic acid addition was 32% of the mass of the two siloxanes.
Example 2:
step 1: (1) ultrasonically dispersing bismuth nitrate in ethylene glycol, and dropwise adding a zinc nitrate solution; ultrasonic homogenization; placing the obtained solution in a microwave reactor, setting the power to be 520WWashing, filtering and drying for 2 minutes; transferring the mixture to a high temperature furnace for setting, setting the temperature to be 500 ℃ and reacting for 1 hour to obtain Zn-Bi2O3. (2) Uniformly mixing tetrabutyl titanate, absolute ethyl alcohol and hydrofluoric acid, adding copper nitrate and cerium nitrate, continuously stirring for 3 hours to obtain a mixed solution, placing the mixed solution into a high-pressure reaction kettle, setting the temperature to be 160 ℃, carrying out hydrothermal reaction for 24 hours, washing, filtering and drying; calcining for 2-3 hours in a high-temperature transfer furnace at the temperature of 400 ℃ under the atmosphere of nitrogen to obtain Ce-Cu-TiO2. (3) Dissolving ammonium metatungstate in deionized water, adding indium nitrate, stirring to form sol, adding polyvinyl alcohol solution, dropwise adding nitric acid, and homogenizing; freeze-drying; and transferring the mixture into a high-temperature box, and calcining the mixture for 4 hours at 450 ℃ to obtain the In-W composite nanoparticles.
Step 2: (1) 22 parts of In-W composite nanoparticles; 12 parts of La2O3(ii) a 2 parts of Y2O3(ii) a 34 parts of B2O3(ii) a 8 parts of SiO2(ii) a 25 parts of Zn-Bi2O3Uniformly mixing to obtain a base material; 15 parts of Ce-Cu-TiO2(ii) a 5 parts of Al2O3(ii) a 1 part of Nb2O5(ii) a 1 part of Ta2O5(ii) a 1 part of Li2Mixing the O uniformly to obtain a functional material; (2) heating and melting the base material at 1400 ℃, preserving heat, and reducing the temperature to 680 ℃; adding functional materials for multiple times, heating to 1500 ℃ again, preserving heat, clarifying, casting in a 670 ℃ mold, preserving heat for 4 hours, and slowly cooling at the set cooling speed of 15 ℃; placing the glass substrate under gamma rays, setting the dose range to be 5 kGy, and irradiating to obtain base glass;
and step 3: (1) cleaning and drying the base glass, placing the base glass in a high-temperature high-pressure reaction kettle containing 2.5mol/L ammonium hydroxide solution, soaking for 4 hours at the set temperature of 100 ℃, washing, and drying by nitrogen; (2) dissolving 3-aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane in ethanol; sequentially adding N-ethyl-N- (3-dimethylpropyl) carbodiimide, N-hydroxysuccinimide and stearic acid; adding silicon dioxide nano particles, and homogenizing to obtain an antireflection solution; (3) spraying an antireflection solution on the surface of the substrate, and drying at 100 ℃; transferring the glass to an atmospheric plasma discharge device, performing dielectric barrier discharge, setting an air gap to be 8mm, and processing for 3 minutes under the voltage of 30V to obtain the high-refractive-index optical glass.
In the scheme, the In-W composite nanoparticles are prepared from the following components In a mass ratio of 0.5: 1 WO3And In2O3And pre-doping to obtain the product. The Zn-Bi2O3Is Bi2O3Doped with Zn2+Thus, the doping amount is 8 wt%; the Ce-Cu-TiO2Is TiO2Middle doped Cu2+And Ce2+Obtained of Cu2+The doping amount is 10wt% and Ce2+The doping amount is 15%. The concentration of the polyvinyl alcohol solution is 4 wt%; the mass ratio of the polyvinyl alcohol solution to the sol is 4: 1. The mass ratio of the 3-aminopropyltriethoxysilane to the gamma-glycidoxypropyltrimethoxysilane is 3: 1; the concentration of the silicon dioxide nano particles in the antireflection solution is 1 g/L; the stearic acid was added in an amount of 30% by mass of the two silicones.
Example 3:
step 1: (1) ultrasonically dispersing bismuth nitrate in ethylene glycol, and dropwise adding a zinc nitrate solution; ultrasonic homogenization; placing the obtained solution in a microwave reactor, setting the power at 520W for reaction for 6 minutes, washing, filtering and drying; transferring the mixture to a high temperature furnace for setting, wherein the setting temperature is 600 ℃, and reacting for 2 hours to obtain Zn-Bi2O3. (2) Uniformly mixing tetrabutyl titanate, absolute ethyl alcohol and hydrofluoric acid, adding copper nitrate and cerium nitrate, continuously stirring for 4 hours to obtain a mixed solution, placing the mixed solution into a high-pressure reaction kettle, setting the temperature to be 160 ℃, carrying out hydrothermal reaction for 24 hours, washing, filtering and drying; calcining for 3 hours in a high temperature furnace at 500 ℃ under nitrogen atmosphere to obtain Ce-Cu-TiO2. (3) Dissolving ammonium metatungstate in deionized water, adding indium nitrate, stirring to form sol, adding polyvinyl alcohol solution, dropwise adding nitric acid, and homogenizing; freeze-drying; and transferring the mixture into a high-temperature box, and calcining the mixture for 4 hours at 550 ℃ to obtain the In-W composite nanoparticles.
Step 2: (1) 30 parts of In-W composite nanoparticles; 18 parts of La2O3(ii) a 4 parts of Y2O3(ii) a 38 parts of B2O3(ii) a 10 parts of SiO2(ii) a 28 parts of Zn-Bi2O3Uniformly mixing to obtain a base material; 20 parts of Ce-Cu-TiO2(ii) a 9 parts of Al2O3(ii) a 5 parts of Nb2O5(ii) a 5 parts of Ta2O5(ii) a 2 parts of Li2Mixing the O uniformly to obtain a functional material; (2) heating and melting the base material at 1500 ℃, preserving heat, and reducing the temperature to 720 ℃; adding functional materials for multiple times, heating to 1600 deg.C, maintaining the temperature, clarifying, casting in a 680 deg.C mold, maintaining the temperature for 5 hr, and slowly cooling at 20 deg.C; placing the glass substrate under gamma rays, setting the dose range to be 10 kGy, and irradiating to obtain base glass;
and step 3: (1) cleaning and drying the base glass, placing the base glass in a high-temperature high-pressure reaction kettle containing 2.5mol/L ammonium hydroxide solution, soaking for 6 hours at the set temperature of 150 ℃, washing, and drying by nitrogen; (2) dissolving 3-aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane in ethanol; sequentially adding N-ethyl-N- (3-dimethylpropyl) carbodiimide, N-hydroxysuccinimide and stearic acid; adding silicon dioxide nano particles, and homogenizing to obtain an antireflection solution; (3) spraying an antireflection solution on the surface of the substrate, and drying at 110 ℃; transferring the glass to an atmospheric plasma discharge device, performing dielectric barrier discharge, setting an air gap to be 8mm, and processing for 5 minutes under the voltage of 30V to obtain the high-refractive-index optical glass.
In the scheme, the In-W composite nanoparticles are prepared from the following components In a mass ratio of 0.7: 1 WO3And In2O3And pre-doping to obtain the product. The Zn-Bi2O3Is Bi2O3Doped with Zn2+Thus, the doping amount is 10 wt%; the Ce-Cu-TiO2Is TiO2Middle doped Cu2+And Ce2+Obtained of Cu2+The doping amount is 15wt% and Ce2+The doping amount is 18%. The concentration of the polyvinyl alcohol solution is 6 wt%; the mass ratio of the polyvinyl alcohol solution to the sol is 4: 1. The mass ratio of the 3-aminopropyltriethoxysilane to the gamma-glycidoxypropyltrimethoxysilane is 4: 1; the silica nanoparticles are inThe concentration of the antireflection solution is 1-1.2 g/L; the stearic acid addition was 35% of the mass of both siloxanes.
Example 4: with reference to the preparation scheme in patent CN112960903A, WO3And In2O3Adding separately; the rest is the same as in example 1.
Example 5: Ce-Cu-TiO2Is not doped with Ce; the rest is the same as in example 1.
Example 6: Ce-Cu-TiO2Not doping Cu; the rest is the same as in example 1.
Example 7: the gamma ray treatment was not performed, and the rest was the same as in example 1.
Example 8: the atmospheric plasma treatment was not performed, and the rest was the same as in example 1.
Experiment: taking the high-refraction optical glass prepared in the embodiment 1-8 to carry out various performance tests, wherein the performance tests comprise refractive index, Abbe number, density and hardness; meanwhile, the glass is subjected to reflectivity detection within a visible wavelength range of 380-780 nm. The data obtained are shown in the following table:
| examples | Refractive index | Abbe number | Density g/cm3 | Hardness x 107pa | Reflectance% |
| Example 1 | 3.2 | 80 | 2.5 | 811 | 1.8 |
| Example 2 | 2.8 | 76 | 2.6 | 809 | 2.0 |
| Example 3 | 2.9 | 75 | 2.8 | 806 | 1.9 |
| Example 4 | 2.8 | 74 | 2.9 | 804 | 1.9 |
| Example 5 | 3.0 | 78 | 3.7 | 736 | 2.2 |
| Example 6 | 2.2 | 68 | 4.0 | 782 | 2.4 |
| Example 7 | 3.0 | 76 | 3.2 | 790 | 1.9 |
| Example 8 | 3.3 | 79 | 2.9 | 808 | 4.2 |
And (4) conclusion: as shown in the data in the table, a high refractive index optical glass having low dispersion and antireflection was prepared in examples 1 to 3. The refractive index in this case is higher compared to the data obtained in patent CN 112960903A. The reason is caused by band gap change caused by metal doping and other element changes.
The data of example 4 are compared with patent CN112960903A, although in the scheme WO3And In2O3The amount of two metals is reduced, but the obtained refractive index is high and the hardness is better. The reason is Zn-Bi2O3The addition of (2) enhances Bi2O3The stability of the glass is enhanced while melting, and Zn-Bi2O3With SiO2Can generate high-refraction low-dispersion high-permeability bismuth silicate crystals, and further enhance the performance and quality of the glass. As well as other variations due to elemental and process variations. Comparing it with example 1, it can be found that: the refractive index and abbe number are significantly reduced because: pre-doping to improve the dipolar interaction between two metals, reform the light absorption band gap, and reduce WO3The refractive index and the light transmittance of the optical glass are further enhanced.
Comparing the data of example 5 with example 1, it can be found that: ce is not doped, resulting in an increase in density with a decrease in strength due to: the effect formed by Ce and Ti ensures that the glass has optical stability, so that the reconstruction of a microstructure can be realized through network depolymerization under the irradiation of the glass, the structural defect is recovered, and the glass has radiation stability. The subsequent irradiation process affects the hardness.
Comparing the data of example 6 with example 1, it can be found that: the Cu is not doped, so that the refractive index is reduced, the dispersion is improved, the density is improved, and the strength is reduced. The reason is that: the effect between Cu and Ti reduces the activation energy in the system, induces the formation of bismuth silicate, accelerates the formation speed, has high growth efficiency and good integrity, thereby enhancing the permeability of visible light wave bands.
Comparing example 7 with example 1, it can be found that: the strength is reduced; the reason is that the gamma ray treatment converts bivalent copper into monovalent copper, promotes the crosslinking of glass networks on the network positions of the original bivalent copper, reduces the average grain diameter in the glass and enhances the strength of the glass. Comparing example 8 with example 1, it can be found that: the reflectance is increased because the roughness is decreased, and the antireflection property, self-cleaning property and acetone resistance of the optical glass are enhanced by utilizing the properties in the antireflection film.
Meanwhile, when the glasses of the embodiment 1 and the embodiment 8 are soaked in the mixed solution for 3 days, substances are separated out from the surface of the embodiment 8, and the aging phenomenon occurs. Whereas no aging occurred in example 1.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A high refractive index optical glass characterized in that: the high-refractive-index optical glass comprises base glass and an anti-reflection coating; the raw material of the base glass contains In-W composite nanoparticles; the In-W composite nanoparticles consist of WO (tungsten oxide) with the mass ratio of (0.5-0.7): 13And In2O3Pre-doping to obtain;
the raw material of the base glass comprises a base material and a functional material; the base material comprises the following components: by weight: 22-30 parts of In-W composite nanoparticles; 12-18 parts of La2O3(ii) a 2-4 parts of Y2O3(ii) a 34 to 38 parts of B2O3(ii) a 8-10 parts of SiO2(ii) a 25 to 28 parts of Zn-Bi2O3(ii) a The functional material comprises the following components: 15-20 parts by weight of Ce-Cu-TiO2(ii) a 5-9 parts of Al2O3(ii) a 1 to 5 parts of Nb2O5(ii) a 1 to 5 parts of Ta2O5(ii) a 1-2 parts of Li2O。
2. A high refractive index optical glass according to claim 1, wherein: the Zn-Bi2O3Is Bi2O3Doped with Zn2+Obtained of Zn2+The doping amount is 8-10 wt%; the Ce-Cu-TiO2Is TiO2Middle doped Cu2+And Ce2+Obtained of Cu2 +The doping amount is 10-15 wt% and Ce2+The doping amount is 15-18%.
3. A preparation method of high-refractive-index optical glass is characterized by comprising the following steps: the method comprises the following steps:
step 1: (1) 22-30 parts of In-W composite nanoparticles; 12-18 parts of La2O3(ii) a 2-4 parts of Y2O3(ii) a 34 to 38 parts of B2O3(ii) a 8-10 parts of SiO2(ii) a 25 to 28 parts of Zn-Bi2O3Uniformly mixing to obtain a base material; 15-20 parts of Ce-Cu-TiO2(ii) a 5-9 parts of Al2O3；1~5 parts of Nb2O5(ii) a 1 to 5 parts of Ta2O5(ii) a 1-2 parts of Li2Mixing the O uniformly to obtain a functional material; (2) heating and melting the base material at 1400-1500 ℃, preserving heat, and reducing the temperature to 680-720 ℃; adding functional materials for multiple times, heating to 1500-1600 ℃, preserving heat, clarifying, casting in a 670-680 ℃ mold, preserving heat for 4-5 hours, and slowly cooling at a cooling speed of 15-20 ℃; placing the glass substrate under gamma rays, setting the dose range to be 5-10 kGy, and irradiating to obtain base glass;
step 2: cleaning and drying the base glass, placing the base glass in a high-temperature high-pressure reaction kettle containing 2.5mol/L ammonium hydroxide solution, soaking for 4-6 hours at the temperature of 100-150 ℃, washing, and drying by nitrogen; spraying an antireflection solution on the surface of the substrate, and drying at 100-110 ℃; and transferring the glass to an atmospheric plasma discharge device, performing dielectric barrier discharge, setting an air gap to be 8mm, and processing for 3-5 minutes under the voltage of 30V to obtain the high-refractive-index optical glass.
4. The method for producing a high refractive index optical glass according to claim 3, wherein: in step 1, the Zn-Bi2O3The preparation method comprises the following steps: ultrasonically dispersing bismuth nitrate in ethylene glycol, and dropwise adding a zinc nitrate solution; ultrasonic homogenization; placing the obtained solution in a microwave reactor, setting the power to 520W, reacting for 2-6 minutes, washing, filtering and drying; transferring the mixture to a high temperature furnace for reaction at 500-600 ℃ for 1-2 hours to obtain Zn-Bi2O3。
5. The method for producing a high refractive index optical glass according to claim 3, wherein: in step 1, the Ce-Cu-TiO2The preparation method comprises the following steps: uniformly mixing tetrabutyl titanate, absolute ethyl alcohol and hydrofluoric acid, adding copper nitrate and cerium nitrate, continuously stirring for 3-4 hours to obtain a mixed solution, placing the mixed solution into a high-pressure reaction kettle, setting the temperature to be 160 ℃, carrying out hydrothermal reaction for 24 hours, washing, filtering and drying; calcining for 2-3 hours in a high-temperature transfer furnace at the temperature of 400-500 ℃ under the atmosphere of nitrogen to obtain Ce-Cu-TiO2。
6. The method for producing a high refractive index optical glass according to claim 3, wherein: in the step 1, the preparation method of the In-W composite nanoparticles comprises the following steps: dissolving ammonium metatungstate in deionized water, adding indium nitrate, stirring to form sol, adding polyvinyl alcohol solution, dropwise adding nitric acid, and homogenizing; freeze-drying; and transferring the mixture into a high-temperature box, and calcining the mixture for 4 hours at the temperature of 450-550 ℃ to obtain the In-W composite nanoparticles.
7. The method for producing a high refractive index optical glass according to claim 6, wherein: the concentration of the polyvinyl alcohol solution is 4-6 wt%; the mass ratio of the polyvinyl alcohol solution to the sol is 4: 1.
8. The method for producing a high refractive index optical glass according to claim 3, wherein: in step 2, the preparation method of the antireflection solution comprises the following steps: dissolving 3-aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane in ethanol; sequentially adding N-ethyl-N- (3-dimethylpropyl) carbodiimide, N-hydroxysuccinimide and stearic acid; adding silicon dioxide nano particles, and homogenizing to obtain an antireflection solution; wherein the mass ratio of the 3-aminopropyltriethoxysilane to the gamma-glycidoxypropyltrimethoxysilane is (3-4) to 1; the concentration of the silicon dioxide nano particles in the antireflection solution is 1-1.2 g/L; the stearic acid accounts for 30-35% of the total mass of the 3-aminopropyltriethoxysilane and the gamma-glycidoxypropyltrimethoxysilane.
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