Nanoparticle reinforced glass ceramic as well as preparation method and application thereof
By adding nanoparticles to glass ceramics and employing hot-pressing and low-temperature sintering technology, the problems of insufficient toughness and hardness of glass ceramics are solved, and high-performance nanoparticle-reinforced glass ceramics are prepared, which are suitable for smart devices and precision instruments.
Patent Information
- Application Number
- CN202511153681.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-18
- Publication Date
- 2025-12-12
AI Technical Summary
Existing glass ceramics have poor fracture toughness and impact resistance, which limits their application in fields such as smart devices and precision instruments. Furthermore, existing strengthening methods have poor controllability, and the grain size and content are uncontrollable.
By adding high-elasticity modulus nano-ceramic particles such as Si3N4, ZrC, and TiB2 and a high-modulus oxide glass matrix, and using hot-pressing and low-temperature sintering technology, the nanoparticles are uniformly distributed in the glass matrix to avoid crystallization, thus preparing high-toughness and high-hardness nanoparticle-reinforced glass ceramics.
Nanoparticle-reinforced glass ceramics with high toughness, high hardness, high wear resistance, and pseudoplastic fracture were prepared, which are suitable for smart devices and precision instruments and have excellent mechanical properties.
Smart Images
Figure CN121107708A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of glass-ceramic materials technology, specifically relating to a nanoparticle-reinforced glass-ceramic, its preparation method, and its application. Background Technology
[0002] Glass ceramics, a direct translation of the English term "glass ceramic," also refers to microcrystalline glass in many studies. It is a multiphase material composed of a crystalline phase and a residual glassy phase, formed after glass undergoes controlled heat treatment to precipitate crystals. Common glass ceramic materials primarily use oxides as raw materials, characterized by high compositional tolerance, readily available raw materials, and ease of molding. Glass ceramics not only possess the characteristics of ordinary glass—low softening point, high mechanical strength, and low coefficient of thermal expansion—but also exhibit excellent impact resistance, corrosion resistance, and superior dielectric properties. Therefore, glass ceramics, as a novel functional material, have become a research hotspot for scholars both domestically and internationally. Various special functions can be obtained by adjusting the composition, leading to their widespread application in fields such as chemistry, biomedicine, aerospace, and microelectronics.
[0003] Conventional glass-ceramics suffer from poor fracture toughness and impact resistance, severely limiting their applications. Ion exchange is commonly used to apply residual compressive stress to the glass-ceramic surface, improving the material's impact resistance. However, this method is generally suitable for thinner materials, such as mobile phone back panels. Another method is crystallization, which uses heat treatment to induce internal crystallization, thereby achieving a strengthening effect. However, this method has poor controllability; grain size and content are uncontrollable, and inhomogeneity exists within the material. Therefore, the strengthening effect is limited.
[0004] Currently, with the widespread use of portable electronic products, the application of glass ceramics in their appearance materials is becoming more and more extensive, and the requirements for the mechanical properties of glass ceramics, such as hardness and strength, are also becoming higher and higher. Therefore, improving the mechanical properties of glass ceramics has become one of the research directions for improving glass performance in recent years. Summary of the Invention
[0005] To address the aforementioned shortcomings, this invention provides a nanoparticle-reinforced glass-ceramic, which possesses high toughness (flexural strength ≥ 200 MPa), high hardness (hardness ≥ 9 GPa), high wear resistance, Young's modulus ≥ 100 GPa, and also exhibits pseudoplastic fracture characteristics.
[0006] Another objective of this invention is to provide a method for preparing the aforementioned nanoparticle-reinforced glass-ceramics. This method involves adding a certain amount of nanoparticles (with high elastic modulus, such as Si3N4, ZrC, TiB2, etc.) and using a high-modulus oxide glass matrix (ZrO2, Al2O3, MgO, etc.); uniformly distributing the nanoceramic particles within the glass matrix; and then using hot pressing and low-temperature sintering to reduce or avoid crystallization of the glass phase matrix. Simultaneously, the nanoparticles do not exhibit dissolution or growth.
[0007] Another object of the present invention is to provide applications of the above-mentioned nanoparticle-reinforced glass-ceramics. These nanoparticle-reinforced glass-ceramics possess high toughness, high hardness, and high wear resistance, and particularly exhibit pseudoplastic fracture characteristics, making them highly valuable for applications in smart devices, ultra-high temperature glass, and precision instruments.
[0008] This invention is achieved through the following technical solution:
[0009] A nanoparticle-reinforced glass ceramic is prepared by mixing oxide powder and low-temperature melting aid powder, heating the mixed powder to a molten state at 1250-1650℃ and holding it at that temperature, then rapidly cooling it in deionized water, and finally refining it by sand milling to obtain glass powder. The glass powder is then mixed with nano-ceramic particles and granulated to obtain mixed glass powder. The mixed glass powder is then molded and hot-pressed at 700-1450℃ under a pressure of 10-30 MPa to obtain the final product.
[0010] Preferably, the mass ratio of the oxide powder to the low-temperature melting aid is (4-5):(0-1), and the amount of the low-temperature melting aid is not 0 in the above ratio. The mass ratio of the mixed glass powder to the nano-ceramic particles is (35-49):(1-15).
[0011] Preferably, the oxide powder is two or more of TiO2, ZrO2, MgO, Al2O3, SiO2, Sc2O3, Cr2O3, and Re2O3.
[0012] More preferably, the Re2O3 is Y2O3, La2O3, Ce2O3 or Sm2O3.
[0013] Preferably, the nano-ceramic particles are one or more of TiN, TiC, ZrC, ZrB2, TiB2, WC, SiC, BN, or Si3N4, and the particle size of the nano-ceramic particles is 50-200 nm.
[0014] Preferably, the low-temperature melting aid is B2O3, CaO, BaO, Na2O, K2O, P2O5, Li2O, ZnO, or PbO.
[0015] Preferably, the nanoparticle-reinforced glass-ceramic has a hardness ≥9 GPa, a flexural strength ≥200 MPa, and a Young's modulus ≥100 GPa.
[0016] The method for preparing the nanoparticle-reinforced glass-ceramic includes the following steps:
[0017] S1. Mix and dry the oxide powder and the low-temperature melting aid to obtain a mixed powder. Heat the mixed powder to a molten state at 1250-1650℃ and keep it at that temperature. Then, cool it quickly in deionized water and refine it in a sand mill to obtain glass powder.
[0018] S2. Mix the glass powder and nano-ceramic particles evenly to obtain a mixed glass powder;
[0019] S3. After molding the mixed glass powder, hot-press and sinter it at 700-1450℃ under a pressure of 10-30MPa to obtain nanoparticle-reinforced glass ceramics.
[0020] Preferably, the heat preservation time in step S1 is 1 to 2 hours.
[0021] The application of the aforementioned nanoparticle-reinforced glass ceramics in the fields of smart devices, semiconductors, or precision instruments.
[0022] Compared with the prior art, the present invention has the following beneficial effects:
[0023] 1. The nanoparticle-reinforced glass-ceramic of the present invention has pseudoplastic fracture, high hardness, high Young's modulus, and high wear resistance, and has great application value in intelligent devices and precision instruments.
[0024] 2. This invention involves adding a certain amount of nanoparticles (with high elastic modulus, such as Si3N4, ZrC, TiB2, etc.) and using a high-modulus oxide glass matrix (ZrO2, Al2O3, MgO, etc.) to uniformly distribute the nano-ceramic particles within the glass matrix. Hot pressing and low-temperature sintering are then employed to reduce or avoid crystallization of the glass matrix. Simultaneously, the nanoparticles do not dissolve or grow, thus enabling the production of high-performance nanoparticle-reinforced glass ceramics. Attached Figure Description
[0025] Figure 1 The image shows the Vickers indentation pattern of the SiC nanoparticle-reinforced SiO2-MgO-Al2O3-ZrO2-Y2O3-B2O3 glass-ceramic of Example 1.
[0026] Figure 2 The image shows the Vickers indentation pattern of the TiB2 nanoparticle-reinforced SiO2-MgO-Al2O3-ZrO2-Y2O3-B2O3 glass-ceramic of Example 2. Detailed Implementation
[0027] The present invention will be further described in detail below with reference to embodiments, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.
[0028] The nano-ceramic particles used in the embodiments of the present invention have a particle size of 50-200 nm.
[0029] Example 1
[0030] 1. Add 38g SiO2 powder, 10g MgO powder, 26g Al2O3 powder, 9g ZrO2 powder, 7g Y2O3 powder, 1g B2O3 powder and grinding balls to anhydrous ethanol and ball mill for 2 hours. The ball-to-powder mass ratio is 2:1 to obtain a uniformly mixed slurry. After drying the slurry at 80℃, pass it through a 100-mesh sieve to obtain a mixed powder.
[0031] 2. Place the mixed powder in a crucible and melt it in air at 1600℃ for 2 hours in a muffle furnace. Then, quench the glass melt in deionized water to obtain glass material, which is then refined by a sand mill to obtain glass powder.
[0032] 3. Add 91 g of glass powder, 10.2 g of SiC powder and grinding balls to anhydrous ethanol and ball mill for 2 h. The mass ratio of ball to powder is 2:1 to obtain a uniformly mixed slurry. After drying the slurry at 80 °C, pass it through a 100-mesh sieve to obtain mixed glass powder.
[0033] 4. The mixed glass powder is molded and then placed into a graphite hot press mold with boron nitride (BN) sprayed on the inner wall. It is then hot-pressed and sintered at 1300℃ for 30 min under a pressure of 10 MPa to obtain 5 vol% SiC nanoparticle-reinforced 95 vol% SiO2-MgO-Al2O3-ZrO2-Y2O3-B2O3 (abbreviated as Si-Mg-Al-Zr-YB) glass ceramic.
[0034] Figure 1 This is a Vickers indentation pattern of the SiC nanoparticle-reinforced SiO2-MgO-Al2O3-ZrO2-Y2O3-B2O3 glass-ceramic from Example 1. From... Figure 1 As can be seen, no cracks appeared at the tip of the Vickers indentation. This indicates that SiO2-MgO-Al2O3-ZrO2-Y2O3-B2O3 glass-ceramic reinforced with SiC nanoparticles has high toughness and strong resistance to crack initiation.
[0035] Example 2
[0036] 1. Add 39.2 g of SiO2 powder, 10.7 g of MgO powder, 27.2 g of Al2O3 powder, 8.9 g of ZrO2 powder, 7 g of Y2O3 powder, 1 g of B2O3 powder and grinding balls to anhydrous ethanol and ball mill for 2 hours. The ball-to-powder mass ratio is 2:1 to obtain a uniformly mixed slurry. After drying the slurry at 80℃, pass it through a 100-mesh sieve to obtain a mixed powder.
[0037] 2. Place the mixed powder in a crucible and melt it in air at 1600℃ for 2 hours in a muffle furnace. Then, quench the glass melt in deionized water to obtain glass material, which is then refined by a sand mill to obtain glass powder.
[0038] 3. Add 92.9 g of glass powder, 7 g of TiB2 powder and grinding balls to anhydrous ethanol and ball mill for 2 h. The mass ratio of ball to powder is 2:1 to obtain a uniformly mixed slurry. After drying the slurry at 80 °C, pass it through a 100-mesh sieve to obtain mixed glass powder.
[0039] 4. After molding the mixed glass powder, it is added into a graphite hot press mold with BN sprayed on the inner wall. The mold is then hot-pressed and sintered at 1200℃ for 30 minutes under a pressure of 10MPa to obtain 95vol% SiO2-MgO-Al2O3-ZrO2-Y2O3-B2O3 (abbreviated as Si-Mg-Al-Zr-YB) glass ceramic reinforced with 5vol% TiB2 nanoparticles.
[0040] Figure 2 This is a Vickers indentation pattern of the TiB2 nanoparticle-reinforced SiO2-MgO-Al2O3-ZrO2-Y2O3-B2O3 glass-ceramic from Example 2. Figure 2 As can be seen, no cracks appeared at the tip of the Vickers indentation. This indicates that TiB2 nanoparticle-reinforced SiO2-MgO-Al2O3-ZrO2-Y2O3-B2O3 glass-ceramic has high toughness and strong resistance to crack initiation.
[0041] Example 3
[0042] 1. Add 36.3 g of SiO2 powder, 10 g of MgO powder, 25.2 g of Al2O3 powder, 8.2 g of ZrO2 powder, 6.5 g of Y2O3 powder, 1 g of B2O3 powder and grinding balls to anhydrous ethanol, and ball mill for 2 hours. The ball-to-powder mass ratio is 2:1 to obtain a uniformly mixed slurry. After drying the slurry at 80℃, pass it through a 100-mesh sieve to obtain a mixed powder.
[0043] 2. Place the mixed powder in a crucible and melt it in air at 1600℃ for 2 hours in a muffle furnace. Then, quench the glass melt in deionized water to obtain glass material, which is then refined by a sand mill to obtain glass powder.
[0044] 3. Add 87.2 g of glass powder, 13.8 g of TiB2 powder and grinding balls to anhydrous ethanol and ball mill for 2 h. The mass ratio of ball to powder is 2:1 to obtain a uniformly mixed slurry. Dry the slurry at 80 °C and pass it through a 100-mesh sieve to obtain mixed glass powder.
[0045] 4. After molding the mixed glass powder, it is added into a graphite hot press mold with BN sprayed on the inner wall. The mixture is then hot-pressed and sintered at 1300℃ for 30 minutes under a pressure of 10MPa to obtain 90vol% SiO2-MgO-Al2O3-ZrO2-Y2O3-B2O3 glass ceramic reinforced with 10vol% TiB2 nanoparticles.
[0046] Example 4
[0047] 1. Add 39.2 g of SiO2 powder, 10.7 g of MgO powder, 27.2 g of Al2O3 powder, 8.9 g of ZrO2 powder, 7 g of Y2O3 powder and grinding balls to anhydrous ethanol, and ball mill for 2 hours. The ball-to-powder mass ratio is 2:1 to obtain a uniformly mixed slurry. Place the slurry in an oven, dry it at 80°C, and then pass it through a 100-mesh sieve to obtain a mixed powder.
[0048] 2. Place the mixed powder in a crucible and melt it in air at 1600℃ for 2 hours in a muffle furnace. Then, quench the glass melt in deionized water to obtain glass material, which is then refined by a sand mill to obtain glass powder.
[0049] 3. Add 93g of glass powder, 7g of TiB2 powder and grinding balls to anhydrous ethanol and ball mill for 2 hours. The mass ratio of ball to powder is 2:1 to obtain a uniformly mixed slurry. After drying the slurry at 80℃, pass it through a 100-mesh sieve to obtain mixed glass powder.
[0050] 4. After the mixed glass powder is molded, it is added into a graphite hot press mold with BN sprayed on the inner wall. It is then hot-pressed and sintered at 1450℃ for 30 minutes under a pressure of 10MPa to obtain 95vol% SiO2-MgO-Al2O3-ZrO2-Y2O3 (abbreviated as Si-Mg-Al-Zr-Y) glass ceramic reinforced with 5vol% TiB2 nanoparticles.
[0051] Example 5
[0052] 1. Add 35.9 g of SiO2 powder, 9.8 g of MgO powder, 24.9 g of Al2O3 powder, 8.1 g of ZrO2 powder, 6.4 g of Y2O3 powder, 1 g of B2O3 powder and grinding balls to anhydrous ethanol and ball mill for 2 hours. The ball-to-powder mass ratio is 2:1 to obtain a uniformly mixed slurry. After drying the slurry at 80℃, pass it through a 100-mesh sieve to obtain a mixed powder.
[0053] 2. Place the mixed powder in a crucible and melt it in air at 1600℃ for 2 hours in a muffle furnace. Then, quench the glass melt in deionized water to obtain glass material, which is then refined by a sand mill to obtain glass powder.
[0054] 3. Add 86.1 g of glass powder, 14.8 g of TiC powder and grinding balls to anhydrous ethanol and ball mill for 2 h. The mass ratio of ball to powder is 2:1 to obtain a uniformly mixed slurry. After drying the slurry at 80 °C, pass it through a 100-mesh sieve to obtain mixed glass powder.
[0055] 4. After the mixed glass powder is molded, it is added into a graphite hot press mold with BN sprayed on the inner wall. It is then hot-pressed and sintered at 1200℃ for 30 minutes under a pressure of 10MPa to obtain 90vol% SiO2-MgO-Al2O3-ZrO2-Y2O3-B2O3 glass ceramic reinforced with 10vol% TiC nanoparticles.
[0056] Comparative Example 1
[0057] 1. Add 42.1 g of SiO2 powder, 11.6 g of MgO powder, 29.2 g of Al2O3 powder, 9.6 g of ZrO2 powder, 7.5 g of Y2O3 powder, 1 g of B2O3 powder and grinding balls to anhydrous ethanol and ball mill for 2 hours. The ball-to-powder mass ratio is 2:1 to obtain a uniformly mixed slurry. Dry the slurry at 80℃ and then pass it through a 100-mesh sieve to obtain a mixed powder.
[0058] 2. Place the mixed powder in a crucible and melt it in air at 1600℃ for 2 hours in a muffle furnace. Then, quench the glass melt in deionized water to obtain glass material, which is then refined by a sand mill to obtain glass powder.
[0059] 3. After molding the glass powder, it is added into a graphite hot press mold with BN sprayed on the inner wall, and sintered at 750℃ for 30 minutes under a pressure of 10MPa to obtain SiO2-MgO-Al2O3-ZrO2-Y2O3-B2O3 glass ceramic.
[0060] Comparative Example 2
[0061] 1. Add 42.1 g of SiO2 powder, 11.6 g of MgO powder, 29.2 g of Al2O3 powder, 9.6 g of ZrO2 powder, 7.5 g of Y2O3 powder and grinding balls to anhydrous ethanol and ball mill for 2 hours. The mass ratio of ball to powder is 2:1 to obtain a uniformly mixed slurry. After drying the slurry at 80℃, pass it through a 100-mesh sieve to obtain a mixed powder.
[0062] 2. Place the mixed powder in a crucible and melt it in air at 1600℃ for 2 hours in a muffle furnace. Then, quench the glass melt in deionized water to obtain glass material, which is then refined by a sand mill to obtain glass powder.
[0063] 3. After molding the glass powder, it is added into a graphite hot press mold with BN sprayed on the inner wall. The mold is then hot-pressed and sintered at 1300℃ for 30 minutes under a pressure of 10MPa to obtain SiO2-MgO-Al2O3-ZrO2-Y2O3 glass ceramic.
[0064] The performance tests of the nanoparticle-reinforced glass ceramics prepared in Examples 1-2 are as follows: (1) Elastic modulus was measured by a nanoindenter; (2) Toughness was tested by indentation method, with a test pressure of 3 kg and a holding time of 10 s; (3) Vickers hardness was measured by Vickers hardness tester, with a test pressure of 3 kg and a holding time of 10 s; (4) Bending strength was measured by three-point bending test, with the strength bar size being 3*4*35 mm and the pressure rate being 0.5 mm / min; (5) Drop resistance was measured by drop test; (6) Fracture type of glass sample was measured by micropillar compression test, with micropillar size being 10 μm high and 4 μm in diameter.
[0065] Table 1. Properties of nanoparticle-reinforced glass-ceramics prepared in Comparative Examples 1-2 and Examples 1-5
[0066]
[0067] Table 1 shows the properties of the nanoparticle-reinforced glass ceramics prepared in Comparative Examples 1-2 and Examples 1-5. As can be seen from Table 1, compared with glass ceramics without added nanoparticles, the nanoparticle-reinforced glass ceramics prepared in Examples 1-5 have higher hardness (hardness ≥ 9 GPa), better wear resistance, higher elastic modulus (Young's modulus ≥ 100 GPa), higher flexural strength (flexural strength ≥ 200 MPa), better impact resistance, and adjustable hardness. Therefore, the nanoparticle-reinforced glass ceramics of this invention simultaneously possess high flexural strength, high hardness, and high wear resistance, and have significant application value in intelligent devices and precision instruments.
[0068] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations and simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.
Claims
1. A nanoparticle-reinforced glass-ceramic, characterized in that, The nanoparticle-reinforced glass-ceramic is prepared by mixing oxide powder and low-temperature melting additive powder; heating the mixed powder to a molten state at 1250-1650℃ and holding it at that temperature, then rapidly cooling it in deionized water, and finally refining it by sand milling to obtain glass powder; then mixing the glass powder with nano-ceramic particles and granulating it to obtain mixed glass powder; and finally molding the mixed glass powder and hot-pressing it at 700-1450℃ under a pressure of 10-30 MPa to obtain the final product.
2. The nanoparticle-reinforced glass-ceramic according to claim 1, characterized in that, The mass ratio of the oxide powder to the low-temperature melting aid is (4-5):(0-1), and the mass ratio of the mixed glass powder to the nano-ceramic particles is (35-49):(1-15).
3. The nanoparticle-reinforced glass-ceramic according to claim 1 or 2, characterized in that, The oxide powder is two or more of TiO2, ZrO2, MgO, Al2O3, SiO2, Sc2O3, Cr2O3, and Re2O3.
4. The nanoparticle-reinforced glass-ceramic according to claim 3, characterized in that, The Re2O3 is Y2O3, La2O3, Ce2O3 or Sm2O3.
5. The nanoparticle-reinforced glass-ceramic according to claim 1 or 2, characterized in that, The nano-ceramic particles are one or more of TiN, TiC, ZrC, ZrB2, TiB2, WC, SiC, BN, or Si3N4, and the particle size of the nano-ceramic particles is 50-200 nm.
6. The nanoparticle-reinforced glass-ceramic according to claim 1 or 2, characterized in that, The low-temperature melting aid is B2O3, CaO, BaO, Na2O, K2O, P2O5, Li2O, ZnO, or PbO.
7. The nanoparticle-reinforced glass-ceramic according to claim 1, characterized in that, The nanoparticle-reinforced glass-ceramic has a hardness ≥9 GPa, a flexural strength ≥200 MPa, and a Young's modulus ≥100 GPa.
8. The method for preparing nanoparticle-reinforced glass-ceramics according to any one of claims 1-7, characterized in that, It includes the following steps: S1. Mix and dry the oxide powder and the low-temperature melting aid to obtain a mixed powder. Heat the mixed powder to a molten state at 1250-1650℃ and keep it at that temperature. Then, cool it quickly in deionized water and refine it in a sand mill to obtain glass powder. S2. Mix the glass powder and nano-ceramic particles evenly to obtain a mixed glass powder; S3. After molding the mixed glass powder, hot-press and sinter it at 700-1450℃ under a pressure of 10-30MPa to obtain nanoparticle-reinforced glass ceramics.
9. The method for preparing nanoparticle-reinforced glass-ceramics according to claim 8, characterized in that, The heat preservation time mentioned in step S1 is 1 to 2 hours.
10. The application of the nanoparticle-reinforced glass ceramic according to any one of claims 1-7 in the fields of smart devices, semiconductors or precision instruments.