A laser protection glass applied to dual wavelengths of 0.53μm and 1.06μm and its preparation method

Abstract

The present invention provides a laser protection glass applicable to dual wavelengths of 0.53 μm and 1.06 μm and a preparation method thereof, belonging to the technical field of preparation of protection glass. The laser protection glass is borosilicate glass, comprising the following components: SiO2 35-47%, Al2O3 1-3%, B2O3 9-13 wt%, Na2O 7-10 wt%, CaO 3-5 wt%, ZnO 3-4 wt%, ZrO2 0.5-1.5 wt%, Er2O3 8-20 wt%, Sm2O3 9-16 wt%. The present invention also provides a preparation method of the laser protection glass applicable to dual wavelengths of 0.53 μm and 1.06 μm. By optimizing the glass components and the melting and annealing processes, the present invention reduces the cracking of the glass generated in the heat treatment process and realizes the protection effect of the glass material at 0.53 μm and 1.06 μm.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparation of protective glass, and particularly relates to a laser protective glass applied to 0.53 μm and 1.06 μm dual wavelengths and a preparation method thereof. Background Art

[0002] Since the invention of lasers in the 1960s, due to their characteristics such as highly concentrated energy and strong directivity, they have been widely used in fields such as machining, scientific research, medical diagnosis, and weaponry. Research shows that lasers with wavelengths in the range of 0.4 - 1.4 μm can cause harm to the human eye. Generally, lasers in the ultraviolet and near-infrared bands can damage the cornea of the human eye, and lasers in the visible light band mainly damage the retina of the human eye. Since the human eye is most sensitive to light with a wavelength near 0.53 μm, when the laser emitted by a 532 nm wavelength Nd:YAG frequency-doubled laser irradiates the human eye, the laser energy density is 150 mJ / cm 2 can burn the retina and cause permanent blindness. In addition, high-energy laser irradiation can damage optical systems such as telescopes, aiming sights, and optical seekers, making them unable to work properly. With the continuous development of laser technology, large-energy, high-power, and short-pulse lasers are increasing day by day, and laser protection has attracted more and more attention, especially the protection technology that can simultaneously protect against multiple wavelengths of lasers.

[0003] Laser protection materials can prevent the human body, instruments and equipment, etc. from being damaged by lasers, which is of great significance in both civilian and military fields. At present, the more commonly used laser protection technologies mainly achieve laser protection by using five principles: absorption, reflection, diffraction, nonlinear optics, and phase change. Among them, absorption-type laser protection materials are the most widely used and can be divided into plastic absorption filters and glass absorption filters. Glass absorption filters use the colored glass body to selectively absorb lasers of specific wavelengths to achieve laser protection. This technology is not affected by the incident angle of the laser and can adapt to observation systems with a large field of view. However, due to factors such as complex manufacturing technology and high product costs, it was once impacted by plastic filters. However, repeated test and use results show that plastic filters can only be used for low-energy laser protection. Under the action of high-energy lasers, plastic filters will exhibit absorption saturation and lose their protection function. Therefore, in recent years, research on glass laser protection materials has been strengthened both at home and abroad. Absorption-type laser protection glass materials can be divided into cut-off absorption type and ion-selective absorption type according to the characteristics of the absorption medium. The so-called cut-off absorption type mainly refers to filter glass with chalcogenide semiconductor compounds such as CdS and CdSe as the absorption medium. The characteristic of this glass is that it can absorb all lasers with wavelengths less than a certain value, while lasers with wavelengths greater than this value can all pass through. Ion-selective absorption type glass materials use the electron transition of a certain valence state in specific ions to absorb lasers of specific wavelengths, thereby achieving the function of laser protection. There are many substances that can absorb lasers that can be added to characteristic absorption type laser protection glass materials. Since the 4f orbitals of rare earth elements are located in the second outermost layer and are shielded to a certain extent by the outer 5s 2 5p 6 shielding and are less affected by surrounding ions, they exhibit narrow line spectrum absorption characteristics and have certain selective absorption characteristics. Therefore, glasses containing rare earth oxides can achieve laser protection functions while ensuring high absorption intensity and high visible light transmittance.

[0004] Most of the research on laser protection glass focuses on the characteristic absorption of a single wavelength of 0.53μm or 1.06μm, and there is less research on glass materials that can simultaneously absorb lasers with wavelengths of 0.53μm and 1.06μm. Liu Xiaodong of Tianjin Polytechnic University prepared 15 single rare earth-doped CaO-SiO2-B2O3-Al2O3-Na2O borosilicate glass samples with a concentration of 1.5mol%, and studied their laser protection characteristics against 532nm high-power lasers through 3 experiments. Meng Xianfeng of Jiangsu University prepared Sm2O3-doped BaO-Al2O3-P2O5-based protection glass, which can be used for laser protection at a wavelength of 1064nm. He Feng of Wuhan University of Technology disclosed a laser protection glass-ceramic material and its preparation method. The obtained glass-ceramic has specific absorption capabilities at multiple laser bands within the wavelength range of 300-1000nm (except for the wavelength ranges of 805-815nm and 975-985nm), making the laser transmittance of the above bands lower than 20%. China National Research Institute of Building Materials Co., Ltd. has determined the formula and glass process of laser glass through a large number of experiments, and the optical density (thickness of 4.0mm) at 532nm and 1064nm reaches 3.3 and 3.4 respectively. In addition, China National Research Institute of Building Materials Co., Ltd. has also studied dual-wavelength laser protection glass with wavelengths of 0.53μm and 1.06μm. In the borosilicate glass containing 30wt% Er2O3 and 30wt% Sm2O3, the optical density values at 532nm and 1064nm are 2.1 and 2.8 respectively, far from meeting the actual requirements of laser protection.

[0005] Due to the large content requirements of two rare earth elements, Er and Sm, in the existing glass formula, when the rare earth content is too high, during the preparation of large-sized glass material samples, crystallization is very likely to occur, resulting in glass devitrification. In addition, due to the short glass melting property, the annealing process is also difficult to master, causing the glass to crack, and finally resulting in a low yield. At the same time, the optical density values of the samples with the existing formula at wavelengths of 0.53μm and 1.06μm are too small to fully meet the protection requirements of the actual scenario. Summary of the Invention

[0006] The purpose of the present invention is to provide a laser protection glass applicable to dual wavelengths of 0.53μm and 1.06μm and its preparation method to solve the problems of crystallization and insufficient protection performance in the preparation process of existing laser protection glass.

[0007] The present invention first provides a laser protection glass applicable to dual wavelengths of 0.53 μm and 1.06 μm. The laser protection glass with dual wavelengths is a borosilicate glass, and in terms of mass percentage, it comprises the following components: 35-47% of SiO2, 1-3% of Al2O3, 9-13 wt% of B2O3, 7-10 wt% of Na2O, 3-5 wt% of CaO, 3-4 wt% of ZnO, 0.5-1.5 wt% of ZrO2, 8-20 wt% of Er2O3, and 9-16 wt% of Sm2O3.

[0008] Preferably, the laser protection glass, in terms of mass percentage, comprises the following components: 38-42% of SiO2, 1.5-2.5% of Al2O3, 10-12 wt% of B2O3, 8-9 wt% of Na2O, 3.5-4.5 wt% of CaO, 3.2-3.8 wt% of ZnO, 0.8-1.2 wt% of ZrO2, 10-15 wt% of Er2O3, and 10-15 wt% of Sm2O3.

[0009] The present invention also provides a preparation method of a laser protection glass applicable to dual wavelengths of 0.53 μm and 1.06 μm, comprising the following steps:

[0010] Step 1: Mix raw materials of high-purity quartz sand, aluminum hydroxide, boric acid, anhydrous sodium carbonate, anhydrous calcium carbonate, zinc oxide, zirconium oxide, erbium oxide, and samarium oxide in proportion to obtain a mixture.

[0011] Step 2: Add the mixture obtained in Step 1 into a high-temperature melting furnace in batches, raise the temperature and continue melting to obtain a glass melt.

[0012] Step 3: Stir the glass melt obtained in Step 2, then lower the temperature and keep it warm.

[0013] Step 4: Let the glass melt after heat preservation in Step 3 stand still, and then discharge the material.

[0014] Step 5: Pour the glass melt discharged in Step 4 into a cast iron mold, after cooling and forming, put it into an annealing furnace for annealing, and cool it with the furnace to obtain a laser protection glass applicable to dual wavelengths of 0.53 μm and 1.06 μm.

[0015] Preferably, the temperature increase in Step 2 is 1500°C - 1550°C, and the melting time is 2 - 4 hours.

[0016] Preferably, the stirring speed in Step 3 is 15 - 30 rpm, and the stirring time is 2 - 4 hours;

[0017] Preferably, the temperature reduction in Step 3 is to 1400°C - 1460°C.

[0018] Preferably, the heat preservation time in step three is 0.5 - 1 hour.

[0019] Preferably, the standing time in step four is 15 - 30 minutes.

[0020] Preferably, the cast iron mold in step five has a preheating temperature of 550°C - 600°C.

[0021] Preferably, the annealing temperature in step five is 600°C - 640°C, and the annealing time is 2 hours.

[0022] Advantages of the present invention

[0023] The present invention provides a laser - protection glass applicable to 0.53μm and 1.06μm dual - wavelengths and a preparation method thereof. The laser - protection glass for the dual - wavelengths, in terms of mass percentage, comprises the following components: SiO2 35 - 47%, Al2O3 1 - 3%, B2O3 9 - 13wt%, Na2O 7 - 10wt%, CaO 3 - 5wt%, ZnO 3 - 4wt%, ZrO2 0.5 - 1.5wt%, Er2O3 8 - 20wt%, Sm2O3 9 - 16wt%. This laser - protection glass simultaneously introduces two rare - earth elements Er2O3 and Sm2O3. Sm has strong absorption at 1075nm, and its absorption spectrum also has a small amount of absorption near 530nm, which can just enhance the absorption of the laser with a wavelength of 0.53μm. Meanwhile, there is no large absorption in the visible - light range, and the average transmittance in the wavelength ranges of 400 - 500nm and 560 - 780nm is 26.54% and 77.94% respectively.

[0024] Meanwhile, the preparation method of the present invention optimizes the glass components, melting, and annealing processes, reduces the cracking of the glass generated in the heat - treatment process, and realizes the protective effect of the glass material at 0.53μm and 1.06μm. As Figure 1 shown in the transmission spectrum diagram of the glass sample, the optical density values calculated according to the transmittance values are 7.48 and 4.21 (4mm thickness) respectively. Brief description of the drawings

[0025] Figure 1 It is the transmission spectrum diagram of the Er2O3 and Sm2O3 co - doped glass prepared in Example 1 of the present invention in the wavelength range of 300 - 1300nm.

[0026] Figure 2 It is the transmission spectrum diagram of the Er2O3 and Sm2O3 co - doped glass prepared in Example 2 of the present invention in the wavelength range of 300 - 1300nm.

[0027] Figure 3Transmission spectrum of the Er2O3 and Sm2O3 co-doped glass prepared in Example 3 of the present invention in the wavelength range of 300 - 1300 nm.

[0028] Figure 4 Transmission spectrum of the Er2O3 and Sm2O3 co-doped glass prepared in Example 4 of the present invention in the wavelength range of 300 - 1300 nm. Detailed implementation manners

[0029] The present invention first provides a laser protection glass applied to dual wavelengths of 0.53 μm and 1.06 μm. The laser protection glass using dual wavelengths is borosilicate glass, and in terms of mass percentage, it includes the following components: SiO2 35 - 47%, Al2O3 1 - 3%, B2O3 9 - 13 wt%, Na2O 7 - 10 wt%, CaO 3 - 5 wt%, ZnO 3 - 4 wt%, ZrO2 0.5 - 1.5 wt%, Er2O3 8 - 20 wt%, Sm2O3 9 - 16 wt%.

[0030] Preferably, the laser protection glass includes the following components in terms of mass percentage: SiO2 38 - 42%, Al2O3 1.5 - 2.5%, B2O3 10 - 12 wt%, Na2O 8 - 9 wt%, CaO 3.5 - 4.5 wt%, ZnO 3.2 - 3.8 wt%, ZrO2 0.8 - 1.2 wt%, Er2O3 10 - 15 wt%, Sm2O3 10 - 15 wt%.

[0031] The present invention also provides a preparation method of a laser protection glass applied to dual wavelengths of 0.53 μm and 1.06 μm, including the following steps:

[0032] Step 1: Mix raw materials of high-purity quartz sand, aluminum hydroxide, boric acid, anhydrous sodium carbonate, anhydrous calcium carbonate, zinc oxide, zirconium oxide, erbium oxide and samarium oxide in proportion to obtain a mixture; the mass ratio of the high-purity quartz sand, aluminum hydroxide, boric acid, anhydrous sodium carbonate, anhydrous calcium carbonate, zinc oxide, zirconium oxide, erbium oxide and samarium oxide is preferably (35.65 - 45):(1 - 2.6):(9 - 13):(7 - 10.4):(3 - 4.5):(3 - 3.7):(0.8 - 1.3):(13 - 20):(9 - 14);

[0033] Step 2: Gradually add the mixture obtained in Step 1 into a platinum crucible of a high-temperature melting furnace until the liquid level of the melt is 2 - 3 cm away from the upper edge of the crucible. The heat preservation temperature of the high-temperature melting furnace is preferably 1350°C - 1400°C. After the feeding is completed, it is preferably heated to 1500°C - 1550°C and continuously melted for 2 - 4 hours to obtain a glass melt;

[0034] Step 3: Stir the glass melt obtained in Step 2. Preferably, a platinum stirring paddle is used to stir the glass melt. The stirring speed is preferably 15 - 30 rpm, and the stirring time is preferably 2 - 4 hours. Then, it is preferably cooled to 1400°C - 1460°C and kept warm for 0.5 - 1 hour. During this step, the stirring paddle continues to stir.

[0035] Step 4: Raise the stirring paddle, and let the glass melt after heat preservation in Step 3 stand still. The standing time is preferably 15 - 30 minutes, and then the material is discharged.

[0036] Step 5: Pour the glass melt discharged in Step 4 into a cast iron mold preheated to 550°C - 600°C. After cooling and forming, it is quickly put into an annealing furnace for annealing, and cooled to room temperature with the furnace. A laser protection glass applicable to 0.53μm and 1.06μm dual wavelengths is obtained. The annealing temperature is preferably 600°C - 640°C, and the annealing time is preferably 2 hours.

[0037] The following further elaborates on the present invention in conjunction with specific embodiments. The raw materials involved in the embodiments are all commercially obtained, and various chemical reagents in the embodiments are of purity above analytical grade.

[0038] Examples 1 - 4

[0039] A method for preparing a dual - wavelength laser protection glass specifically includes the following steps:

[0040] (1) The chemical reagent raw materials are fully mixed according to the following table ratio and sieved through a 40 - mesh sieve for later use.

[0041] Example 1 Example 2 Example 3 Example 4 High-purity quartz sand (99%) 45.00 47.00 43.00 35.65 Aluminum hydroxide (99.9%) 1.00 2.00 2.60 1.50 Boric acid (99.9%) 9.00 10.50 12.00 13.00 Anhydrous sodium carbonate (99.9%) 10.00 9.00 10.4 7.00 Anhydrous calcium carbonate (99.9%) 3.00 4.00 4.50 4.35 Zinc oxide (99.9%) 3.00 3.20 3.70 3.45 Zirconium oxide (99.9%) 1.00 1.30 0.80 1.05 Erbium oxide (99.9%) 18.00 13.00 14.00 20.00 Samarium oxide (99.9%) 10.00 10.00 9.00 14.00

[0042] (2) The fully - mixed glass batch is added to a platinum crucible placed in a high - temperature melting furnace in portions until the liquid level of the melt is 2 - 3 cm away from the upper edge of the crucible. The heat - preservation temperature of the high - temperature melting furnace is 1370°C.

[0043] (3) After the feeding is completed, the temperature is raised to 1550°C and melting is continued for 3 hours.

[0044] (4) A platinum stirring paddle stirs the glass melt. After stirring at a speed of 15 rpm for 1.5 hours, it is stirred at a speed of 25 rpm for 1.5 hours.

[0045] (5) After the temperature of the high - temperature melting furnace is cooled to 1400°C, it is kept warm for 0.5 hour. During this step, the platinum stirring paddle continues to stir at a speed of 25 rpm.

[0046] (6) Raise the stirring paddle, and let the glass melt stand still for 15 minutes and then discharge the material.

[0047] (7) The glass melt is poured into a cast iron mold preheated to 600 °C. After cooling and forming, it is quickly placed in an annealing furnace at 640 °C for annealing for 2 hours, and then cooled to room temperature with the furnace to obtain the laser protection glass.

[0048] The transmission spectra of the co-doped glasses prepared in Examples 1-4 in the wavelength range of 300-1300 nm are as Figures 1-4 shown, and the specific data are shown in Table 1.

[0049] Table 1

[0050]

[0051] Example 5

[0052] Steps (1)-(5) are the same as those in Examples 1-4.

[0053] (6) Raise the stirring paddle, let the glass melt stand for 30 minutes and then discharge.

[0054] (7) The glass melt is poured into a cast iron mold preheated to 600 °C. After cooling and forming, it is quickly placed in an annealing furnace at 640 °C for annealing for 2 hours, and then cooled to room temperature with the furnace to obtain the laser protection glass.

[0055] Example 6

[0056] Steps (1)-(6) are the same as those in Examples 1-4.

[0057] (7) The glass melt is poured into a cast iron mold preheated to 600 °C. After cooling and forming, it is quickly placed in an annealing furnace at 620 °C for annealing for 2 hours, and then cooled to room temperature with the furnace to obtain the laser protection glass.

[0058] Example 7

[0059] Steps (1)-(2), (5)-(7) are the same as those in Examples 1-4.

[0060] (3) After adding materials, raise the temperature to 1550 °C and continue melting for 2 hours.

[0061] (4) Use a platinum stirring paddle to stir the glass melt. Stir at a speed of 15 rpm for 1 hour and then stir at a speed of 25 rpm for 1 hour;

[0062] Example 8

[0063] Steps (1)-(2), (5)-(7) are the same as those in Examples 1-4.

[0064] (3) After adding materials, raise the temperature to 1550 °C and continue melting for 4 hours.

[0065] (4) The platinum stirring paddle stirs the glass melt. After stirring at a speed of 15 rpm for 2 hours, it stirs at a speed of 25 rpm for 2 hours.

[0066] The embodiments of the present invention have been introduced in detail above. Specific examples are used in this article to elaborate on the principle and implementation manner of the present invention. The description of the above embodiments is only used to help understand the method and its core idea of the present invention; at the same time, for those of ordinary skill in the art, according to the idea of the present invention, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation to the present invention.

Claims

1. A laser protection glass applicable to dual wavelengths of 0.53μm and 1.06μm, characterized in that, The laser protection glass using dual wavelengths is borosilicate glass, which, by weight percentage, comprises the following components: SiO2 35-47%, Al2O3 1-3%, B2O3 9-13 wt%, Na2O 7-10 wt%, CaO 3-5 wt%, ZnO 3-4 wt%, ZrO2 0.5-1.5 wt%, Er2O3 10-20 wt%, Sm2O3 10-16 wt%.

2. The laser protection glass applied to the dual wavelengths of 0.53μm and 1.06μm according to claim 1, wherein The laser protection glass described above, by weight percentage, comprises the following components: SiO2 38-42%, Al2O3 1.5-2.5%, B2O3 10-12 wt%, Na2O 8-9 wt%, CaO 3.5-4.5 wt%, ZnO 3.2-3.8 wt%, ZrO2 0.8-1.2 wt%, Er2O3 10-15 wt%, Sm2O3 10-15 wt%.

3. The preparation method of a laser protection glass applied to 0.53μm and 1.06μm dual wavelengths according to claim 1 or 2, characterized in that, It includes the following steps: Step 1: Mix high-purity quartz sand, aluminum hydroxide, boric acid, anhydrous sodium carbonate, anhydrous calcium carbonate, zinc oxide, zirconium oxide, erbium oxide and samarium oxide as raw materials in proportion to obtain a mixed material; Step 2: Add the mixed material from Step 1 into a high-temperature melting furnace in batches, raise the temperature and continue melting to obtain a glass melt; Step 3: Stir the glass melt from Step 2, then lower the temperature and keep it warm; Step 4: Let the glass melt after heat preservation in Step 3 stand still and then discharge the material; Step 5: Pour the glass melt discharged in Step 4 into a cast iron mold. After cooling and forming, put it into an annealing furnace for annealing and cool with the furnace to obtain the laser protection glass applied to dual wavelengths of 0.53 μm and 1.06 μm.

4. The preparation method of a laser protection glass applied to 0.53μm and 1.06μm dual wavelengths according to claim 3, characterized in that, The temperature increase in Step 2 is 1500°C - 1550°C, and the melting time is 2-4 hours.

5. The preparation method of a laser protection glass applied to 0.53μm and 1.06μm dual wavelengths according to claim 3, characterized in that, The stirring speed in Step 3 is 15-30 rpm, and the stirring time is 2-4 hours.

6. The preparation method of a laser protection glass applied to 0.53μm and 1.06μm dual wavelengths according to claim 3, characterized in that, The temperature reduction in Step 3 is to reduce to 1400°C - 1460°C.

7. The preparation method of a laser protection glass applied to 0.53μm and 1.06μm dual wavelengths according to claim 3, characterized in that, The heat preservation time in Step 3 is 0.5-1 hour.

8. The preparation method of a laser protection glass applied to 0.53μm and 1.06μm dual wavelengths according to claim 3, characterized in that, The standing time in Step 4 is 15-30 minutes.

9. The preparation method of a laser protection glass applied to 0.53μm and 1.06μm dual wavelengths according to claim 3, characterized in that, The preheating temperature of the cast iron mold in Step 5 is 550°C - 600°C.

10. The preparation method of a laser protection glass applied to 0.53μm and 1.06μm dual wavelengths according to claim 3, characterized in that, The annealing temperature in Step 5 is 600°C - 640°C, and the annealing time is 2 hours.

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