Infrared glass surface treatment method
By employing a two-step method involving silver ion treatment and annealing, the surface hardness of chalcogenide glass is significantly improved, solving the problem of easy damage to chalcogenide glass, enhancing its application capability in harsh environments, and without affecting its optical performance.
Patent Information
- Application Number
- CN202511909615.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-17
- Publication Date
- 2026-03-06
Smart Images
Figure CN121609519A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of glass surface treatment technology, specifically, it relates to an infrared glass surface treatment method. Background Technology
[0002] Chalcogenide glasses have an infrared transmission band that covers the entire mid-infrared to long-infrared region, making them ideal infrared window and lens materials. Compared with infrared crystal materials such as single-crystal germanium (Ge) and zinc sulfide (ZnS), they have outstanding advantages such as strong designability of optical parameters, low manufacturing cost, and the ability to be processed into aspherical surfaces.
[0003] However, chalcogenide glasses also suffer from low hardness, stemming from their inherent weak chemical bonds and loose three-dimensional network structure. This manifests as chalcogenide glasses being easily scratched, brittle, difficult to polish, and having poor abrasion resistance, severely impacting their reliability, lifespan, and optical performance stability in harsh environments. Furthermore, the actual strength of the glass is far lower than its theoretical strength. This is primarily due to surface cracks, where stress concentration at the crack tips leads to breakage. Therefore, surface treatment to create a compressive stress layer on the glass surface to inhibit crack initiation and propagation, thereby enhancing its performance, is essential.
[0004] Increased hardness enhances the resistance of infrared chalcogenide glasses to indentation, scratching, and abrasion. Currently, methods for improving glass surface hardness primarily include physical vapor deposition (PEVDC) (such as depositing hard films) and chemical strengthening (such as ion exchange). PEVDC methods present challenges related to film-substrate adhesion, matching thermal expansion coefficients, and potential impact on infrared transmittance. Chemical strengthening essentially involves ion exchange, where larger ions displace smaller ions from the glass surface. This ion exchange creates a volume difference on the glass surface, resulting in a "clogging" phenomenon and forming a compressive stress layer. After glass strengthening, the propagation of surface cracks is not only resisted by the glass's internal network structure but also by the compressive stress layer formed after chemical strengthening, which resists the initiation and propagation of microcracks.
[0005] Traditional chemical strengthening methods (such as potassium-sodium ion exchange for soda-lime glass) usually require high temperatures, while chalcogenide glasses have relatively low transition temperatures (Tg), and high-temperature treatment may lead to crystallization, deformation, or deterioration of their optical properties.
[0006] Arsenic selenide chalcogenide glasses, due to their excellent infrared transmittance, high refractive index, and low phonon energy, have broad application prospects in infrared thermal imaging, optical sensing, and laser transmission. However, these glasses generally suffer from insufficient mechanical properties, particularly low surface hardness and susceptibility to scratches, which severely limits their application in practical optical components, especially their durability in harsh environments.
[0007] Therefore, developing a method that is suitable for low Tg (183℃) chalcogenide glasses in the As-Se system, with a mild process and can significantly improve their surface hardness, is of great significance to the technological development of infrared glass. Summary of the Invention
[0008] The purpose of this invention is to provide a simple, mild, and effective method for improving the surface hardness of arsenic selenide chalcogenide glass, which can effectively enhance its surface microhardness.
[0009] The objective of this invention can be achieved through the following technical solutions: An infrared glass surface treatment method includes the following steps: 1. Pretreatment: The arsenic selenide chalcogenide glass is cut and polished to the optical surface, and then ultrasonically cleaned with organic solvent and deionized water in sequence to remove surface contaminants, and then dried for later use.
[0010] 2. Preparation of silver ion treatment solution: Prepare an aqueous solution of silver nitrate (AgNO3) as the silver ion treatment solution.
[0011] 3. Polishing treatment of chalcogenide glass: Polish the glass after pretreatment in step (1) using the silver nitrate aqueous solution prepared in step (2).
[0012] 4. After polishing, immerse the glass in a silver nitrate aqueous solution. After removing the glass from the solution, dry it with nitrogen gas.
[0013] 5. After steps (3) and (4), the surface-dried, silver-ion-polished As-Se chalcogenide glass is placed in an annealing furnace for annealing treatment to complete the surface treatment process of the glass.
[0014] 6. Surface microhardness tests were performed on the treated As-Se chalcogenide glass, and the results showed that the hardness increased by 13%~17% after treatment.
[0015] Furthermore, the organic solvent mentioned in step (1) is acetone, ethanol, etc.
[0016] Furthermore, the mass concentration of the nitrate aqueous solution in step (2) is 5%~20%.
[0017] Furthermore, the polishing time in step (3) is 5 to 30 minutes.
[0018] Furthermore, in step (4), the soaking temperature is 20~30℃ and the time is 1~24 hours.
[0019] Furthermore, in step (4), the preferred soaking temperature is 25~30℃, and the preferred soaking time is 4~12 hours.
[0020] Furthermore, in step (5), the annealing temperature is 100~180℃ and the treatment time is 1~24 hours.
[0021] Furthermore, in step (5), the preferred annealing temperature is 150~180℃, and the preferred time is 5~20 hours.
[0022] Based on the above technical solutions, the present invention has the following key technical points: 1) Ag ions were selected as the surface chemical strengthening ions for As-Se chalcogenide glasses. Polishing and immersion of the infrared glass using a silver ion-containing solution, especially surface polishing with a silver-containing solution, facilitated rapid ion diffusion and exchange under relatively mild conditions. The As-Se chalcogenide glass structure is dominated by a three-dimensional network of covalent bonds. The covalent bond radius of As is 120 pm, and that of Se is 116 pm. The covalent bond radius of Ag is 134 pm, and its ionic radius is 126 pm. Therefore, whether silver replaces As atoms in ionic or atomic form or is incorporated into the interstitial spaces of the As-Se glass framework, it achieves a larger replacement of surface atoms, thereby generating compressive stress on the glass surface after chemical strengthening.
[0023] 2) A two-step method is adopted, involving polishing and immersion followed by annealing. This method achieves chemical strengthening at a relatively mild temperature below the chalcogenide glass transition temperature, avoiding the risks of oxidation and crystallization of chalcogenide glasses. The preparation process is mild and effective.
[0024] 3) After surface treatment, the surface microhardness of As-Se glass increased by 13%~17%, which is a significant improvement in hardness.
[0025] The beneficial effects of this invention are: 1. Significantly improves hardness: After treatment by the method of this invention, the micro Vickers hardness (HV) of the glass surface can be increased by 13% to 17% or more, which greatly enhances its scratch resistance and wear resistance.
[0026] 2. Mild process: The entire process is carried out in a low-temperature environment (far below the Tg point of the glass), avoiding the risk of glass crystallization, deformation or oxidation caused by high-temperature treatment.
[0027] 3. Maintaining optical performance: The modified layer is extremely thin, limited to a few micrometers on the surface, and has minimal impact on key optical properties such as the infrared transmittance of the glass body.
[0028] 4. Simple operation and low cost: The required equipment is simple, the reagents are common, and it is easy to achieve large-scale production. Attached Figure Description
[0029] The invention will now be further described with reference to the accompanying drawings.
[0030] Figure 1 This is a microhardness characterization diagram of the As-Se chalcogenide glass sample before treatment; Figure 2 This is a microhardness characterization image of the As-Se chalcogenide glass sample after treatment in Example 1; Figure 3 This is a microhardness characterization image of the As-Se chalcogenide glass sample after treatment in Example 2; Figure 4 This is a microhardness characterization image of the As-Se chalcogenide glass sample after treatment in Example 3; Figure 5 This is a microhardness characterization image of the As-Se chalcogenide glass sample after treatment in Example 4; Figure 6 This is a microhardness characterization image of the As-Se chalcogenide glass sample after treatment in Example 5; Figure 7 This is a microhardness characterization image of the As-Se chalcogenide glass sample after treatment in Example 6; Figure 8 This is a microhardness characterization diagram of the As-Se chalcogenide glass sample after treatment in Comparative Example 1; Figure 9 This is a microhardness characterization diagram of the As-Se chalcogenide glass sample after treatment in Comparative Example 2. Detailed Implementation
[0031] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0032] Example 1 The surface treatment of the arsenic selenide chalcogenide glass sample includes the following steps: Step 1: Cut and polish the arsenic selenide chalcogenide glass sample to the optical surface, then use organic solvents (such as acetone and ethanol) and deionized water in sequence for ultrasonic cleaning to remove surface contaminants, and then dry it for later use.
[0033] Step 2: Polish the chalcogenide glass sample with a 10% silver nitrate aqueous solution. Polishing time is 10 minutes.
[0034] Step 3: Immerse the polished glass sample in a silver nitrate aqueous solution. The treatment temperature is 25℃, and the treatment time is 1 hour. After removing the sample from the solution, dry it with nitrogen gas.
[0035] Step 4: Place the dried, silver-ion-polished As-Se chalcogenide glass into an annealing furnace for annealing. The treatment temperature is 180℃, and the treatment time is 24 hours.
[0036] Step 5: Perform surface microhardness testing on the treated As-Se chalcogenide glass and compare the results with those before treatment; for example... Figure 1 and Figure 2 The figures shown are microhardness characterization diagrams of the As-Se chalcogenide glass samples before and after treatment. The hardness before treatment is HV=119, and the hardness after treatment is HV=138. The hardness increased by 15.97% after surface treatment.
[0037] Example 2 The surface treatment of the arsenic selenide chalcogenide glass sample includes the following steps: Step 1: Cut and polish the arsenic selenide chalcogenide glass sample to the optical surface, then use organic solvents (such as acetone and ethanol) and deionized water in sequence for ultrasonic cleaning to remove surface contaminants, and then dry it for later use.
[0038] Step 2: Polish the chalcogenide glass sample with a 20% silver nitrate aqueous solution. Polishing time is 5 minutes.
[0039] Step 3: Immerse the polished glass sample in a silver nitrate aqueous solution. The treatment temperature is 25℃, and the treatment time is 1 hour. After removing the sample from the solution, dry it with nitrogen gas.
[0040] Step 4: Place the dried, silver-ion-polished As-Se chalcogenide glass into an annealing furnace for annealing. The treatment temperature is 180℃, and the treatment time is 24 hours.
[0041] Step 5: Perform surface microhardness testing on the treated As-Se chalcogenide glass and compare the results with those before treatment; for example... Figure 1 and Figure 3 The figures shown are microhardness characterization diagrams of the As-Se chalcogenide glass samples before and after treatment. The hardness before treatment is HV=119, and the hardness after treatment is HV=140. The hardness increased by 17.65% after surface treatment.
[0042] Example 3 The surface treatment of the arsenic selenide chalcogenide glass sample includes the following steps: Step 1: Cut and polish the arsenic selenide chalcogenide glass sample to the optical surface, then use organic solvents (such as acetone and ethanol) and deionized water in sequence for ultrasonic cleaning to remove surface contaminants, and then dry it for later use.
[0043] Step 2: Polish the chalcogenide glass sample with a 15% silver nitrate aqueous solution. Polishing time is 30 minutes.
[0044] Step 3: Immerse the polished glass sample in a silver nitrate aqueous solution. The treatment temperature is 25℃, and the treatment time is 1 hour. After removing the sample from the solution, dry it with nitrogen gas.
[0045] Step 4: Place the dried, silver-ion-polished As-Se chalcogenide glass into an annealing furnace for annealing. The treatment temperature is 100℃, and the treatment time is 5 hours.
[0046] Step 5: Perform surface microhardness testing on the treated As-Se chalcogenide glass and compare the results with those before treatment; for example... Figure 1 and Figure 4 The figures shown are microhardness characterization images of the As-Se chalcogenide glass samples before and after treatment. The hardness before treatment is HV=119, and the hardness after treatment is HV=137. The hardness increased by 15.13% after surface treatment.
[0047] Example 4 The surface treatment of the arsenic selenide chalcogenide glass sample includes the following steps: Step 1: Cut and polish the arsenic selenide chalcogenide glass sample to the optical surface, then use organic solvents (such as acetone and ethanol) and deionized water in sequence for ultrasonic cleaning to remove surface contaminants, and then dry it for later use.
[0048] Step 2: Polish the chalcogenide glass sample with a 5% (w / w) silver nitrate aqueous solution. Polishing time is 5 minutes.
[0049] Step 3: Immerse the polished glass sample in a silver nitrate aqueous solution. The treatment temperature is 30℃, and the treatment time is 6 hours. After removing the sample from the solution, dry it with nitrogen gas.
[0050] Step 4: Place the dried, silver-ion-polished As-Se chalcogenide glass into an annealing furnace for annealing. The treatment temperature is 180℃, and the treatment time is 10 hours.
[0051] Step 5: Perform surface microhardness testing on the treated As-Se chalcogenide glass and compare the results with those before treatment; for example... Figure 1 and Figure 5 The figures shown are microhardness characterization diagrams of the As-Se chalcogenide glass samples before and after treatment. The hardness before treatment is HV=119, and the hardness after treatment is HV=135. The hardness increased by 13.45% after surface treatment.
[0052] Example 5 The surface treatment of the arsenic selenide chalcogenide glass sample includes the following steps: Step 1: Cut and polish the arsenic selenide chalcogenide glass sample to the optical surface, then use organic solvents (such as acetone and ethanol) and deionized water in sequence for ultrasonic cleaning to remove surface contaminants, and then dry it for later use.
[0053] Step 2: Polish the chalcogenide glass sample with a 20% silver nitrate aqueous solution. Polishing time is 10 minutes.
[0054] Step 3: Immerse the polished glass sample in a silver nitrate aqueous solution. The treatment temperature is 30℃, and the treatment time is 8 hours. After removing the sample from the solution, dry it with nitrogen gas.
[0055] Step 4: Place the dried, silver-ion-polished As-Se chalcogenide glass into an annealing furnace for annealing. The treatment temperature is 100℃, and the treatment time is 20 hours.
[0056] Step 5: Perform surface microhardness testing on the treated As-Se chalcogenide glass and compare the results with those before treatment; for example... Figure 1 and Figure 6 The figures shown are microhardness characterization diagrams of the As-Se chalcogenide glass samples before and after treatment. The hardness before treatment is HV=119, and the hardness after treatment is HV=140. The hardness increased by 17.65% after surface treatment.
[0057] Example 6 The surface treatment of the arsenic selenide chalcogenide glass sample includes the following steps: Step 1: Cut and polish the arsenic selenide chalcogenide glass sample to the optical surface, then use organic solvents (such as acetone and ethanol) and deionized water in sequence for ultrasonic cleaning to remove surface contaminants, and then dry it for later use.
[0058] Step 2: Polish the chalcogenide glass sample with a 15% silver nitrate aqueous solution. Polishing time is 5 minutes.
[0059] Step 3: Immerse the polished glass sample in a 15% (w / w) silver nitrate aqueous solution. The treatment temperature is 25℃, and the treatment time is 1 hour. After removing the sample from the solution, dry it with nitrogen gas.
[0060] Step 4: Place the dried, silver-ion-polished As-Se chalcogenide glass into an annealing furnace for annealing. The treatment temperature is 150℃, and the treatment time is 10 hours.
[0061] Step 5: Perform surface microhardness testing on the treated As-Se chalcogenide glass and compare the results with those before treatment; for example... Figure 1 and Figure 7 The figures shown are microhardness characterization diagrams of the As-Se chalcogenide glass samples before and after treatment. The hardness before treatment is HV=119, and the hardness after treatment is HV=136. The hardness increased by 14.29% after surface treatment.
[0062] Comparative Example 1 The surface treatment of the arsenic selenide chalcogenide glass sample includes the following steps: Step 1: Cut and polish the arsenic selenide chalcogenide glass sample to the optical surface, then use organic solvents (such as acetone and ethanol) and deionized water in sequence for ultrasonic cleaning to remove surface contaminants, and then dry it for later use.
[0063] Step 2: Polish the chalcogenide glass sample with a 15% silver nitrate aqueous solution. Polishing time is 5 minutes.
[0064] Step 3: Immerse the polished glass sample in a silver nitrate aqueous solution. The treatment temperature is 25℃, and the treatment time is 1 hour. After removing the sample from the solution, dry it with nitrogen gas.
[0065] Step 4: Place the dried, silver-ion-polished As-Se chalcogenide glass into an annealing furnace for annealing treatment. The treatment temperature is 80℃, and the treatment time is 24 hours.
[0066] Step 5: Perform surface microhardness testing on the treated As-Se chalcogenide glass and compare the results with those before treatment; for example... Figure 1 and Figure 8 The figures shown are microhardness characterization images of the As-Se chalcogenide glass samples before and after treatment. The hardness before treatment is HV=119, and the hardness after treatment is HV=133. The hardness increased by 11.76% after surface treatment.
[0067] Comparative Example 2 The surface treatment of the arsenic selenide chalcogenide glass sample includes the following steps: Step 1: Cut and polish the arsenic selenide chalcogenide glass sample to the optical surface, then use organic solvents (such as acetone and ethanol) and deionized water in sequence for ultrasonic cleaning to remove surface contaminants, and then dry it for later use.
[0068] Step 2: Polish the chalcogenide glass sample with a 10% silver nitrate aqueous solution. Polishing time is 5 minutes.
[0069] Step 3: Immerse the polished glass sample in a silver nitrate aqueous solution. The treatment temperature is 25℃, and the treatment time is 1 hour. After removing the sample from the solution, dry it with nitrogen gas.
[0070] Step 4: Place the dried, silver-ion-polished As-Se chalcogenide glass into an annealing furnace for annealing. The treatment temperature is 150℃, and the treatment time is 0.5 hours.
[0071] Step 5: Perform surface microhardness testing on the treated As-Se chalcogenide glass and compare the results with those before treatment; for example... Figure 1 and Figure 9 The figures shown are microhardness characterization diagrams of the As-Se chalcogenide glass samples before and after treatment. The hardness before treatment is HV=119, and the hardness after treatment is HV=131. The hardness increased by 10.08% after surface treatment.
[0072] The summary of the microhardness and hardness increase percentage of the samples in the above embodiments and comparative examples is shown in Table 1 below: Table 1 As can be seen from the above embodiments and comparative examples, within the scope of protection of this invention, the percentage increase in hardness in the specific embodiments is between 13% and 17%, while the percentage increase in hardness in the comparative examples is between 10% and 11%. The increase in hardness is significantly affected by the temperature and time of the annealing treatment.
[0073] The above detailed embodiments provide a specific description of the analytical methods involved in this invention. It should be noted that the above description is only intended to help those skilled in the art better understand the methods and ideas of this invention, and is not intended to limit the scope of the invention. Without departing from the principles of this invention, those skilled in the art can make appropriate adjustments or modifications to this invention, and such adjustments and modifications should also fall within the protection scope of this invention.
Claims
1. An infrared glass surface treatment method characterized by, The method comprises the following steps:
1. Pre-treatment: cutting and polishing the arsenic-selenium chalcogenide glass to an optical surface, and then sequentially performing ultrasonic cleaning using an organic solvent and deionized water, and drying for standby; 2. Preparation of silver ion treatment solution: preparing an aqueous silver nitrate solution as a silver ion treatment solution; 3. Polishing treatment of chalcogenide glass: polishing the glass after pre-treatment in step (1) using the aqueous silver nitrate solution prepared in step (2); 4. After polishing is completed, the glass is immersed in the aqueous silver nitrate solution, and after the glass is taken out of the solution, the glass is blown dry with nitrogen; 5. After steps (3) and (4), the As-Se chalcogenide glass with a dry surface and silver ion polishing is placed in an annealing furnace for annealing treatment, and the surface treatment process of the glass is completed.
2. The method of claim 1, wherein the infrared glass surface is a surface of a glass window of an automobile. The organic solvent in step (1) comprises acetone and ethanol.
3. The method of claim 1, wherein the infrared glass surface is a surface of a glass window of a vehicle. The mass concentration of the aqueous nitrate salt solution in step (2) is 5% to 20%.
4. The method of claim 1 wherein the infrared glass surface is a surface of a glass window of an automobile. The polishing time in step (3) is 5 to 30 minutes.
5. The method of claim 1 wherein the infrared glass surface is a surface of a glass window of an automobile. The immersion treatment temperature in step (4) is 20 to 30 DEG C, and the time is 1 to 24 hours.
6. The method of claim 5, wherein the infrared glass surface is treated by a method comprising: The immersion temperature in step (4) is 25 to 30 DEG C, and the time is 4 to 12 hours.
7. The method of claim 1 wherein the infrared glass surface is a surface of a window. The annealing treatment temperature in step (5) is 100 to 180 DEG C, and the treatment time is 1 to 24 hours.
8. The method of claim 7, wherein the infrared glass surface is treated by a method comprising: The annealing treatment temperature in step (5) is 150 to 180 DEG C, and the time is 5 to 20 hours.