CN110698062B - Radiation-resistant fluorophosphate glass - Google Patents

Abstract

The invention relates to a novel optical glass, in particular to a radiation-resistant fluorophosphate glass. It solves the problems of large weight and volume of the existing optical system with radiation resistance. Features, the refractive index n _d value is 1.515873 ~ 1.516834, the dispersion value is 0.0065 ~ 0.0073, and has high radiation resistance, can withstand 1 × 10 ⁴ rad (Si) ~ 1 × 10 ⁵ rad (Si) gamma rays Irradiation, the irradiation dose rate is 40rad(Si)/s. It can replace the negative lens glass material in the prior art, and its special dispersion performance is not only conducive to eliminating the chromatic aberration and spherical aberration of the optical system, but also more conducive to the lightweight and miniaturization of high-resolution aerospace devices.

Description

A radiation-resistant fluorophosphate glass

technical field

The invention relates to a novel optical glass, in particular to a radiation-resistant fluorophosphate optical glass.

Background technique

When the optical system is operating in space, due to encountering high-energy electromagnetic radiation, such as ultraviolet rays, χ-rays, γ-rays, etc., the optical glass material in the system produces induced color centers, causing glass coloring, and in severe cases, the transmission of the entire system. The rate of rapid decay or even opacity, which greatly deteriorates the imaging quality of the optical system, makes the satellite control system unable to detect effective stellar targets, and causes the entire satellite control system to fail, unable to provide long-term stable flight attitude control for the satellite system.

Using radiation-resistant optical glass with the same optical constant with radiation-resistant properties to replace ordinary optical glass materials of the same brand can significantly improve the radiation performance of the optical system and greatly prolong the service life of the optical system in space. The optical system usually adopts the combination of positive and negative lenses to eliminate system chromatic aberration (eg CN101995643, CN102354042). The negative lens glass materials are mostly composed of one or more flint glasses (belonging to high refractive index and high dispersion materials) with radiation resistance properties. However, the weight and volume of such optical systems are relatively large, which is not conducive to the operation of high-resolution lightweight aerospace devices. If a low-refractive-index and low-dispersion glass material with radiation resistance characteristics is used to replace the above-mentioned negative lens glass material, the special dispersion properties of this material are not only conducive to eliminating chromatic aberration and spherical aberration of the optical system, but also conducive to high Lightweighting and miniaturization of high-resolution aerospace devices.

SUMMARY OF THE INVENTION

In order to solve the problems of large weight and volume of the existing optical system with radiation resistance, the present invention provides a composition of radiation-resistant fluorophosphate glass and a preparation method thereof. The low-dispersion glass material replaces the negative lens glass material in the prior art, and its special dispersion properties are not only conducive to eliminating chromatic aberration and spherical aberration of the optical system, but also more conducive to the lightweight and miniaturization of high-resolution aerospace devices.

The technical solution of the present invention is to provide a radiation-resistant fluorophosphate glass, which is special in that it has the characteristics of low refractive index and low dispersion, which helps to eliminate the chromatic aberration and spherical aberration of the optical system, and its refractive index n The _d value is 1.515873～1.516834, and the dispersion value is 0.0065～0.0073;

The composition of this kind of glass material is shown in the following table in wt%:

In the above composition, the metaphosphate is mainly Ba(PO ₃ ) ₂ , and Ba(PO ₃ ) ₂ and Al(PO ₃ can be partially replaced by Ca(PO ₃ ) ₂ , Mg(PO ₃ ) ₂ , KPO ₃ , NaPO ₃ ) ₃ and LiPO ₃ , but in a proportion not exceeding 14 wt%. Ba(PO ₃ ) ₂ can improve the anti-devitrification property of the material, and at the same time, the ultraviolet intrinsic absorption cut-off wavelength of the glass material is shifted to the short wavelength direction. Al(PO ₃ ) ₃ has a lower refractive index and a larger Abbe number, and its introduction makes the ultraviolet partial dispersion of the glass lower. When the components in the fluorine-phosphorus glass are mainly metaphosphate, the glass network structure is mainly based on phosphorus-oxygen tetrahedron PO ₄ , and an appropriate amount of fluoride, such as AlF ₃ , BaF ₂ , SrF ₂ , ZnF ₂ , LiF can be added. Improve the glass network structure, improve the stability of the glass, help to inhibit the devitrification of the glass. The glass network structure can vary greatly with the F/P ratio and with the cations introduced, such as the formation of (PO ₃ )F or PO _n F _4-n .

Adding CeO ₂ as a stabilizer to glass can significantly improve the radiation resistance of optical materials. The essential reason is that after the optical glass is subjected to high-energy radiation, the high-speed electrons first interact with Ce ⁴⁺ ions to form Ce ³⁺ ions, namely Ce ⁴⁺ +e→Ce ³⁺ , thereby reducing the microstructure of the glass. Defect formation. The presence of F ^- ions (due to the introduction of fluoride) is beneficial to increase the Ce ⁴⁺ /Ce ³⁺ concentration ratio in the glass.

The above-mentioned more suitable composition of the present invention contains by weight percentage:

The above-mentioned more suitable composition of the present invention contains by weight percentage:

The above-mentioned more suitable composition of the present invention contains by weight percentage:

The above-mentioned more suitable composition of the present invention contains by weight percentage:

The above-mentioned preferred composition of the present invention contains by weight percentage:

The above-mentioned preferred composition of the present invention contains by weight percentage:

Fluorophosphorus glass has high temperature volatilization during the melting process, which is easy to change the composition, so a certain amount of compensation needs to be considered in the melting process. In order to obtain high-quality radiation-resistant fluorophosphate glass with consistent performance, the formulation of melting process parameters is very critical. Therefore, the present invention also provides a preparation method of radiation-resistant fluorophosphate glass. The above-mentioned raw materials are weighed and mixed uniformly according to the composition ratio. When the temperature of the melting furnace rises to 780-950° C., the mixture is gradually added in several times to oxidize Put it in an aluminum crucible, and cover it to melt the raw materials. The heating time is 1h to 1.5h; then continuously stir, clarify and homogenize the glass liquid for 1h to 1.5h; after the furnace temperature drops to 600 to 700 °C, pour it into the mold and pour it. After completion, carry out precision annealing treatment, wherein the heating rate is 1.0-2.5°C/min, the temperature is raised to 450°C-500°C for 4h-5h, and then the temperature is lowered to room temperature at 1.0-2.0°C/min. The fluorophosphoric acid optical glass sample was obtained after optical cold working. The refractive index n _d value of the sample obtained by testing is 1.515873-1.516834, and the dispersion value υ _d is 0.0065-0.0073.

Further, in step 2, the temperature of the crucible melting furnace is 850°C; the heating time of the raw material compound is 1.5h; the time for stirring, clarifying and homogenizing the glass liquid is 1h; in step 3, the furnace temperature is lowered to 650°C; /min, keep at 450°C for 5h, and then drop to room temperature at 1.0°C/min.

The advantages of the present invention are:

The radiation-resistant fluorophosphate glass provided by the invention has the characteristics of high optical transmittance (up to 90%), low refractive index and low dispersion in a wide spectral band range (300nm-2000nm), and the refractive index n _d value is 1.515873 ～1.516834, the dispersion value is 0.0065～0.0073, and it has high radiation resistance, can withstand 1×10 ⁴ rad(Si)～1×10 ⁵ rad(Si) gamma ray irradiation, and the irradiation dose rate is 40rad (Si)/s. It can replace the negative lens glass material in the prior art, and its special dispersion performance is not only conducive to eliminating the chromatic aberration and spherical aberration of the optical system, but also more conducive to the lightweight and miniaturization of high-resolution aerospace devices.

Description of drawings

Fig. 1 is the transmittance curve of Example undecafluorophosphate glass (without CeO ₂ ) and radiation-resistant fluorophosphate glass (with CeO ₂ );

Fig. 2 is the transmittance curve of radiation-resistant fluorophosphate glass (containing CeO ₂ ) before and after 50Krad(Si) γ-ray irradiation dose;

Fig. 3 is the transmittance curve of radiation-resistant fluorophosphate glass (containing CeO ₂ ) before and after 100K rad(Si) γ-ray irradiation dose;

Detailed ways

The present invention will be further described below with reference to the accompanying drawings and specific embodiments.

Example 1

The composition of the glass of the present embodiment is as follows:

This example prepared radiation resistant fluorophosphate glass by the following method:

Step 1: Weigh 800g of the above-mentioned raw material compounds according to the composition ratio, and mix them evenly;

Step 2: When the temperature of the crucible furnace rises to 780°C, gradually add the uniformly mixed raw material compound in step 1 into the alumina crucible in several times, and cover the lid to melt the raw material compound, and the heating time is 1 h; Homogenize the glass liquid for 1h;

Step 3: After cooling to 600°C, pour it into the mold, and perform annealing treatment after the pouring is completed, wherein the heating rate is 1.0°C/min, the temperature is raised to 450°C for 4 hours, and then the temperature is lowered to room temperature at 1.0°C/min. After optical cold processing After that, fluorophosphoric acid optical glass is obtained.

The fluorophosphate glass developed in this example has high radiation resistance, its refractive index _nd value is 1.516834, and its dispersion value is 0.006837.

Embodiment 2

The composition of the glass of the present embodiment is as follows:

This example prepared radiation resistant fluorophosphate glass by the following method:

Step 1. Weigh 850g of the above-mentioned raw material compounds according to the composition ratio, and mix them uniformly;

Step 2: When the temperature of the crucible melting furnace rises to 800°C, gradually add the uniformly mixed raw material compound in step 1 into the alumina crucible in several times, and cover the lid to melt the raw material compound, and the heating time is 1.5h; Clarify and homogenize the glass liquid for 1h;

Step 3: After cooling to 650°C, pour it into the mold, and perform annealing treatment after the casting is completed. The heating rate is 1.5°C/min, the temperature is raised to 450°C for 4 hours, and then the temperature is lowered to room temperature at 1.2°C/min. After optical cold processing After that, fluorophosphoric acid optical glass is obtained.

The fluorophosphate glass developed in this example has high radiation resistance, its refractive index _nd value is 1.515873, and its dispersion value is 0.007041.

Embodiment 3

The composition of the glass of the present embodiment is as follows:

This example prepared radiation resistant fluorophosphate glass by the following method:

Step 1. Weigh 850g of the above-mentioned raw material compounds according to the composition ratio, and mix them uniformly;

Step 2: When the temperature of the crucible melting furnace rises to 850°C, the uniformly mixed raw material compound in step 1 is gradually added to the alumina crucible in several times, and the lid is covered to melt the raw material compound, and the heating time is 1h; then continue to stir and clarify , Homogenize the glass liquid for 1.5h;

Step 3: After cooling to 680°C, pour it into the mold, and perform annealing treatment after the pouring is completed. The heating rate is 1.5°C/min, the temperature is raised to 500°C for 4 hours, and then the temperature is lowered to room temperature at 1.5°C/min. After optical cold processing After that, fluorophosphoric acid optical glass is obtained.

The fluorophosphate glass developed in this example has high radiation resistance, its refractive index _nd value is 1.516527, and its dispersion value is 0.007308.

Embodiment 4

The composition of the glass of the present embodiment is as follows:

This example prepared radiation resistant fluorophosphate glass by the following method:

Step 1. Weigh 850g of the above-mentioned raw material compounds according to the composition ratio, and mix them uniformly;

Step 2: When the temperature of the crucible melting furnace rises to 880°C, gradually add the uniformly mixed raw material compound in step 1 into the alumina crucible in several times, and cover the lid to melt the raw material compound, and the heating time is 1h; then continue to stir and clarify , Homogenize the glass liquid for 1h;

Step 3: After cooling to 680°C, pour it into the mold, and perform annealing treatment after the pouring is completed, wherein the heating rate is 2.0°C/min, the temperature is raised to 500°C for 5 hours, and then the temperature is lowered to room temperature at 1.5°C/min. After optical cold processing After that, fluorophosphoric acid optical glass is obtained.

The fluorophosphate glass developed in this example has high radiation resistance, its refractive index _nd value is 1.516294, and its dispersion value is 0.006574.

Embodiment 5

The composition of the glass of the present embodiment is as follows:

This example prepared radiation resistant fluorophosphate glass by the following method:

Step 1. Weigh 850g of the above-mentioned raw material compounds according to the composition ratio, and mix them uniformly;

Step 2: When the temperature of the crucible melting furnace rises to 900°C, gradually add the uniformly mixed raw material compound in step 1 into the alumina crucible in several times, and cover the lid to melt the raw material compound, and the heating time is 1h; then keep stirring and clarifying , Homogenize the glass liquid for 1h;

Step 3: After cooling to 700°C, pour it into the mold, and perform annealing treatment after the pouring is completed. The heating rate is 2.0°C/min, the temperature is raised to 450°C for 4 hours, and then the temperature is lowered to room temperature at 1.5°C/min. After optical cold processing After that, fluorophosphoric acid optical glass is obtained.

The fluorophosphate glass developed in this example has high radiation resistance, its refractive index _nd value is 1.515943, and its dispersion value is 0.006994.

Embodiment 6

The composition of the glass of the present embodiment is as follows:

This example prepared radiation resistant fluorophosphate glass by the following method:

Step 1. Weigh 850g of the above-mentioned raw material compounds according to the composition ratio, and mix them uniformly;

Step 2: When the temperature of the crucible melting furnace rises to 900°C, gradually add the uniformly mixed raw material compound in step 1 into the alumina crucible in several times, and cover the lid to melt the raw material compound, and the heating time is 1h; then keep stirring and clarifying , Homogenize the glass liquid for 1h;

Step 3: After cooling to 700°C, pour it into the mold, and perform annealing treatment after the pouring is completed, wherein the heating rate is 2.5°C/min, the temperature is raised to 450°C for 4 hours, and then the temperature is lowered to room temperature at 1.5°C/min. After optical cold processing After that, fluorophosphoric acid optical glass is obtained.

The fluorophosphate glass developed in this example has high radiation resistance, its refractive index _nd value is 1.516029, and its dispersion value is 0.006599.

Embodiment 7

The composition of the glass of the present embodiment is as follows:

This example prepared radiation resistant fluorophosphate glass by the following method:

Step 1. Weigh 850g of the above-mentioned raw material compounds according to the composition ratio, and mix them uniformly;

Step 2: When the temperature of the melting furnace of the crucible rises to 950°C, gradually add the uniformly mixed raw material compound in step 1 into the alumina crucible in several times, and cover the lid to melt the raw material compound, and the heating time is 1h; then keep stirring and clarifying , Homogenize the glass liquid for 1h;

Step 3: After cooling to 700°C, pour it into the mold, and perform annealing treatment after the pouring is completed, wherein the heating rate is 2.5°C/min, the temperature is raised to 450°C for 4 hours, and then the temperature is lowered to room temperature at 1.5°C/min. After optical cold processing After that, fluorophosphoric acid optical glass is obtained.

The fluorophosphate glass developed in this example has high radiation resistance, its refractive index _nd value is 1.515982, and its dispersion value is 0.006729.

Embodiment 8

The composition of the glass of the present embodiment is as follows:

This example prepared radiation resistant fluorophosphate glass by the following method:

Step 1. Weigh 850g of the above-mentioned raw material compounds according to the composition ratio, and mix them uniformly;

Step 2: When the temperature of the melting furnace of the crucible rises to 950°C, gradually add the uniformly mixed raw material compound in step 1 into the alumina crucible in several times, and cover the lid to melt the raw material compound, and the heating time is 1h; then keep stirring and clarifying , Homogenize the glass liquid for 1h;

Step 3: After cooling to 700°C, pour it into the mold, and perform annealing treatment after the pouring is completed. The heating rate is 2.5°C/min, the temperature is raised to 450°C for 4 hours, and then the temperature is lowered to room temperature at 2.0°C/min. After optical cold processing After that, fluorophosphoric acid optical glass is obtained.

The fluorophosphate glass developed in this example has high radiation resistance, its refractive index _nd value is 1.516829, and its dispersion value is 0.007159.

Embodiment 9

The composition of the glass of the present embodiment is as follows:

This example prepared radiation resistant fluorophosphate glass by the following method:

Step 1. Weigh 850g of the above-mentioned raw material compounds according to the composition ratio, and mix them uniformly;

Step 2: When the temperature of the melting furnace of the crucible rises to 950°C, gradually add the uniformly mixed raw material compound in step 1 into the alumina crucible in several times, and cover the lid to melt the raw material compound, and the heating time is 1h; then keep stirring and clarifying , Homogenize the glass liquid for 1h;

Step 3: After cooling to 700°C, pour it into the mold, and perform annealing treatment after the pouring is completed. The heating rate is 2.5°C/min, the temperature is raised to 450°C for 4 hours, and then the temperature is lowered to room temperature at 2.0°C/min. After optical cold processing After that, fluorophosphoric acid optical glass is obtained.

The fluorophosphate glass developed in this example has high radiation resistance, its refractive index _nd value is 1.516432, and its dispersion value is 0.006825.

Embodiment ten

The composition of the glass of the present embodiment is as follows:

This example prepared radiation resistant fluorophosphate glass by the following method:

Step 1. Weigh 850g of the above-mentioned raw material compounds according to the composition ratio, and mix them uniformly;

Step 2: When the temperature of the melting furnace of the crucible rises to 950°C, gradually add the uniformly mixed raw material compound in step 1 into the alumina crucible in several times, and cover the lid to melt the raw material compound, and the heating time is 1h; then keep stirring and clarifying , Homogenize the glass liquid for 1h;

Step 3: After cooling to 700°C, pour it into the mold, and perform annealing treatment after the pouring is completed. The heating rate is 2.5°C/min, the temperature is raised to 450°C for 4 hours, and then the temperature is lowered to room temperature at 2.0°C/min. After optical cold processing After that, fluorophosphoric acid optical glass is obtained.

The fluorophosphate glass developed in this example has high radiation resistance, its refractive index _nd value is 1.516357, and its dispersion value is 0.007036.

Embodiment 11

The composition of the glass of the present embodiment is as follows:

This example prepared radiation resistant fluorophosphate glass by the following method:

Step 1. Weigh 850g of the above-mentioned raw material compounds according to the composition ratio, and mix them uniformly;

Step 2: When the temperature of the melting furnace of the crucible rises to 950°C, gradually add the uniformly mixed raw material compound in step 1 into the alumina crucible in several times, and cover the lid to melt the raw material compound, and the heating time is 1h; then keep stirring and clarifying , Homogenize the glass liquid for 1h;

Step 3: After cooling to 700°C, pour it into the mold, and perform annealing treatment after the pouring is completed. The heating rate is 2.5°C/min, the temperature is raised to 450°C for 4 hours, and then the temperature is lowered to room temperature at 2.0°C/min. After optical cold processing After that, fluorophosphoric acid optical glass is obtained.

It can be seen from the above table that by adjusting the glass composition, the fluorophosphate glass developed by the present invention has high radiation resistance, the refractive index n _d value is 1.515873-1.516834, and the dispersion value is 0.0065-0.0073. As shown in FIG. 1 , the fluorophosphate glass (containing no CeO ₂ ) provided in the eleventh embodiment of the present invention and the fluorophosphate glass (containing CeO ₂ ) provided by other embodiments are in a wide band range (300nm～2000nm) It has high optical transmittance (up to 90%); it can be seen from Figure 2 and Figure 3 that the radiation-resistant fluorophosphate glass (containing CeO ₂ ) provided by the present invention has high radiation resistance and can withstand 1 ×10 ⁴ rad(Si)～1×10 ⁵ rad(Si) gamma ray irradiation, and the irradiation dose rate is 40 rad(Si)/s.

Claims (2)

1. A radiation-resistant fluorophosphate glass, characterized in that: refractive index n_dValue 1.515873, dispersion value 0.007041;

the compositions in weight percent wt% are shown in the following table:

2. a radiation-resistant fluorophosphate glass, characterized in that: refractive index n_dValue 1.516294, dispersion value 0.006574;

the compositions in weight percent wt% are shown in the following table:

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