Nanoparticle reinforced glass ceramic as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of oxide glass ceramic materials, and discloses nano-particle reinforced glass ceramic as well as a preparation method and application thereof. The nano-particle reinforced glass ceramic is prepared by the following steps: pressing mixed powder of oxide powder, nano-particles and a low-temperature melting aid to obtain a biscuit; and heating the biscuit to a molten state at 1200-2700 DEG C by adopting a suspension method, and cooling to obtain the product. The nano-particle reinforced glass ceramic has high hardness of more than or equal to 8GPa, high toughness of more than or equal to 6MPa * m < 1 / 2 >, high wear resistance, high drop resistance and the like, particularly has the pseudoplastic fracture characteristic and adjustable transparency, has the maximum visible light transmittance of 84%, and can be applied to the fields of intelligent equipment, ultrahigh-temperature glass or precision instruments and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of glass-ceramic materials. Specifically, it relates to a nano-particle reinforced glass-ceramic and its preparation method and application. Background Art

[0002] Glass-ceramic, also known as glass ceramics, is a polycrystalline solid-phase material containing a vitreous body prepared by controlled nucleation and crystallization at a certain temperature. It has good mechanical properties, adjustable thermal expansion properties, thermal shock resistance, corrosion resistance, etc., and is widely used in electronic devices, aerospace, chemistry, biomedicine, construction and other fields. Especially with the popularization of 5G and wearable devices, it is required that the appearance materials use non-metallic materials. Compared with structural ceramic materials, glass-ceramics have low cost, high wear resistance, no signal shielding, and good mechanical properties, and are very suitable for application in electronic products.

[0003] The elastic modulus is a measure of the ability of a material to resist deformation. The larger the elastic modulus, the greater the rigidity and the greater the stress required for elastic deformation. Generally, increasing the elastic modulus of glass-ceramics is beneficial to improving the strength, hardness and wear resistance of the material. The elastic modulus of high-alumina-silica glass is 60 - 75 GPa, and the elastic modulus of lithium-alumina-silica glass is 75 - 85 GPa. The elastic modulus of glass-ceramics is less than 100 GPa. Conventional glass-ceramics are prepared through processes such as high-temperature melting, forming, heat treatment, and strengthening treatment. CN110546115A discloses an ion-strengthened glass-ceramic containing SiO2, Al2O3, MgO, Li2O, Y2O3, B2O3, P2O5, Na2O, K2O, CaO, SrO, BaO, ZnO, TiO2, ZrO2. The elastic modulus is 90 GPa, and it is 0.82 MPa*m 1 / 2 and the Vickers hardness is 650 kgf / mm 2 . CN112876067A discloses an oxide high-entropy glass including TiO2, ZrO2, Y2O3, Al2O3 and a fifth oxide. By using the pneumatic suspension melting method, a high-hardness and high Young's modulus oxide high-entropy glass is obtained, with a hardness ≥ 8 GPa and an elastic modulus ≥ 100 GPa. Therefore, increasing the elastic modulus of glass-ceramics is one of the effective ways to improve the comprehensive performance. However, adding reinforcing phases (nano-particles, fibers), high-modulus raw materials (ZrO2, Al2O3, etc.) will promote the crystallization of the glass phase, resulting in performance degradation. Summary of the Invention

[0004] In order to solve the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a nano-particle reinforced glass-ceramic. This nano-particle reinforced glass-ceramic simultaneously has high hardness (≥ 8 GPa), high toughness (≥ 6 MPa*m 1 / 2 , and can reach up to 17 MPa*m 1 / 2) High wear resistance, drop resistance, etc., especially with the characteristics of pseudoplastic fracture and adjustable transparency.

[0005] Another object of the present invention is to provide a method for preparing the above-mentioned nanoparticle-reinforced glass-ceramics. This method involves adding nanoparticle reinforcing agents (high elastic modulus, low thermal expansion coefficient, such as TiB2, TiC, WC, etc.) and high-modulus oxides (ZrO2, Al2O3, MgO, etc.); adopting containerless melting-solidification treatment to reduce the contact between the high-temperature melt and the container wall, inhibit heterogeneous nucleation, enable the melt to obtain a deep undercooling degree, and avoid the crystallization of the glass phase, thereby obtaining high-performance nanoparticle-reinforced glass-ceramics.

[0006] Another object of the present invention is to provide the application of the above-mentioned nanoparticle-reinforced glass-ceramics.

[0007] The object of the present invention is achieved by the following technical solutions:

[0008] A nanoparticle-reinforced glass-ceramic is obtained by pressing a mixed powder of oxide powder, nanoparticles, and low-temperature melting aids with a mass ratio of (50 - 99.5):(0.5 - 40):(0 - 15) to obtain a green body; and then using a suspension method to heat the green body to a molten state at 1200 - 2700 °C and then cooling it.

[0009] Preferably, the mass ratio of the oxide powder, nanoparticles, and low-temperature melting aids is (75 - 90):(2 - 30):(5 - 10).

[0010] Preferably, the oxide powder is two or more of TiO2, ZrO2, HfO2, MgO, Al2O3, SiO2, Sc2O3, Cr2O3, Re2O3.

[0011] Preferably, the Re2O3 is Y2O3, La2O3, Ce2O3, or Sm2O 3。

[0012] Preferably, the nanoparticles are one or more of TiN, TiC, Ti(C,N), ZrB2, TiB2, WC, SiC, TaC, TaN, or Si3N4.

[0013] Preferably, the low-temperature melting aids are B2O3, CaO, BaO, Na2O, K2O, P2O5, Li2O, SrO, ZnO, or PbO.

[0014] Preferably, the hardness of the above-mentioned nanoparticle-reinforced glass-ceramics is ≥8 GPa, and the toughness is ≥6 MPa*m 1 / 2 And the maximum transmittance in the visible light is 84%.

[0015] The preparation method of the described nanoparticle-reinforced glass ceramic comprises the following steps:

[0016] S1. Mix and dry the oxide powder, nanoparticles and low-temperature melting aids to obtain a mixed powder;

[0017] S2. Cold isostatically press the mixed powder at a pressure of 100 - 200 MPa to form a green body;

[0018] S3. Use a suspension method to melt the green body at 1200 - 2700 °C to a molten state, and then obtain the nanoparticle-reinforced glass ceramic through cooling.

[0019] Preferably, the suspension method described in step S3 is pneumatic suspension, electromagnetic suspension or electrostatic suspension.

[0020] The application of the described nanoparticle-reinforced glass ceramic in intelligent devices, ultra-high temperature glass or precision instruments.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1. The nanoparticle-reinforced glass ceramic of the present invention simultaneously has high toughness, high hardness, high wear resistance, etc., and particularly has the characteristics of pseudoplastic fracture and adjustable transparency, and has great application value in intelligent devices, ultra-high temperature glass and precision instruments.

[0023] 2. The present invention adopts containerless melting-solidification treatment, reduces the contact between the high-temperature melt and the container wall, inhibits heterogeneous nucleation, enables the melt to obtain a deep undercooling degree, and avoids the crystallization of the glass phase. The nano-ceramic particles complete self-diffusion in the glass melt by thermal motion and are uniformly dispersed in the glass matrix. Thus, a high-performance nanoparticle-reinforced glass ceramic is prepared. Description of the Drawings

[0024] Figure 1 It is a physical photograph of the TiB2 nanoparticle-reinforced Y2O3-Al2O3 glass ceramic in Example 1;

[0025] Figure 2 It is a physical photograph of the SiC nanoparticle-reinforced Si-Mg-Al-Zr-Y glass ceramic in Example 2;

[0026] Figure 3 It is a TEM photograph of the WC nanoparticle-reinforced Si-Mg-Al-Zr-Y glass ceramic in Example 3;

[0027] Figure 4 It is a Vickers indentation diagram of the TiB2 nanoparticle-reinforced Si-Mg-Al-Zr-Y glass ceramic in Example 4. Detailed Embodiments

[0028] The present invention will be further described in detail below in conjunction with embodiments, but the implementation manners 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 stated, the reagents, methods and equipment adopted in the present invention are conventional reagents, methods and equipment in the technical field of the present invention.

[0029] Example 1: TiB2 Nanoparticle Reinforced Y-Al Glass Ceramic

[0030] 1. Add 44 g of Y2O3 powder, 56 g of Al2O3 powder, and 5 g of TiB2 nanoparticles into absolute ethanol and ultrasonically disperse for 10 min; then put it into a grinding ball mill and mill for 2 h with a ball-to-material ratio of 1:2 to obtain a uniformly mixed slurry; put the slurry into a rotary evaporator, dry at 80 °C and then pass through a 60-mesh sieve to obtain a mixed powder.

[0031] 2. Dry-press the mixed powder using a steel mold under a pressure of 30 MPa to obtain a block with the corresponding shape, and then perform cold isostatic pressing under a pressure of 200 MPa to obtain a green body.

[0032] 3. Heat the green body to the molten state at 2700 °C by the suspension method, and then perform a cooling treatment at a cooling rate of 250 K / s to obtain TiB2 nanoparticle reinforced Y2O3-Al2O3 glass ceramic.

[0033] Figure 1 is a physical photograph of the TiB2 nanoparticle reinforced Y2O3-Al2O3 glass ceramic in Example 1; as can be seen from Figure 1 it, after adding TiB2 nanoparticles, the glass ceramic Y2O3-Al2O3 is bright black.

[0034] Example 2: SiC Nanoparticle Reinforced Si-Mg-Al-Zr-Y Glass Ceramic

[0035] 1. Add 40 g of SiO2 powder, 11 g of MgO powder, 28 g of Al2O3 powder, 9 g of ZrO2 powder, 7 g of Y2O3 powder, and 5 g of SiC nanoparticles into absolute ethanol and ultrasonically disperse for 10 min; then put it into a grinding ball mill and mill for 2 h with a ball-to-material ratio of 1:2 to obtain a uniformly mixed slurry; put the slurry into a rotary evaporator, dry at 80 °C and then pass through a 60-mesh sieve to obtain a mixed powder.

[0036] 2. Dry-press the mixed powder using a steel mold under a pressure of 30 MPa to obtain a block with the corresponding shape, and then perform cold isostatic pressing under a pressure of 200 MPa to obtain a green body.

[0037] 3. The green body is heated to the molten state at 2000 °C by the suspension method, and then cooled at a cooling rate of 250 K / s to obtain SiC nanoparticle-reinforced Si-Mg-Al-Zr-Y glass-ceramics.

[0038] Figure 2 is the physical photo of the SiC nanoparticle-reinforced Si-Mg-Al-Zr-Y glass-ceramics in Example 2; It can be seen from Figure 2 that after adding SiC nanoparticles, the glass-ceramics Si-Mg-Al-Zr-Y is still transparent.

[0039] Example 3 WC nanoparticle-reinforced Si-Mg-Al-Zr-Y glass-ceramics

[0040] 1. 40 g of SiO2 powder, 11 g of MgO powder, 28 g of Al2O3 powder, 9 g of ZrO2 powder, 7 g of Y2O3 powder, and 5 g of WC nanoparticles are added to absolute ethanol and ultrasonically dispersed for 10 min; then put into a grinding ball mill for ball milling for 2 h, and the ball-to-material ratio is 1:2 to obtain a uniformly mixed slurry; the slurry is put into a rotary evaporator, dried at 80 °C and sieved through a 60-mesh sieve to obtain a mixed powder;

[0041] 2. The mixed powder is dry-pressed into a block with the corresponding shape by a steel mold under a pressure of 30 MPa, and then cold isostatically pressed into a green body under a pressure of 200 MPa;

[0042] 3. The green body is heated to the molten state at 2050 °C by the suspension method, and then cooled at a cooling rate of 250 K / s to obtain WC nanoparticle-reinforced Si-Mg-Al-Zr-Y glass-ceramics.

[0043] Figure 3 is the TEM photo of the WC nanoparticle-reinforced Si-Mg-Al-Zr-Y glass-ceramics in Example 3; It can be seen from Figure 3 that after adding WC nanoparticles, no crystallization of the Si-Mg-Al-Zr-Y glass-ceramics is caused, and the matrix is still the glass phase.

[0044] Example 4 TiB2 nanoparticle-reinforced Si-Mg-Al-Zr-Y glass-ceramics

[0045] 1. 40 g of SiO2 powder, 11 g of MgO powder, 28 g of Al2O3 powder, 9 g of ZrO2 powder, 7 g of Y2O3 powder, and 20 g of TiB2 nanoparticles are added to absolute ethanol and ultrasonically dispersed for 10 min; then put into a grinding ball mill for ball milling for 2 h, and the ball-to-material ratio is 1:2 to obtain a uniformly mixed slurry; the slurry is put into a rotary evaporator, dried at 80 °C and sieved through a 60-mesh sieve to obtain a mixed powder;

[0046] 2. Dry press the mixed powder using a steel mold at a pressure of 30 MPa to obtain a block of the corresponding shape, and then perform cold isostatic pressing at a pressure of 200 MPa to obtain a green body;

[0047] 3. Use the suspension method to heat the green body to the molten state at 2200 °C, and then perform a cooling treatment at a cooling rate of 250 K / s to obtain TiB2 nanoparticle-reinforced Si-Mg-Al-Zr-Y glass-ceramics.

[0048] Figure 4 It is the Vickers indentation diagram of TiB2 nanoparticle-reinforced Si-Mg-Al-Zr-Y glass-ceramics in Example 4. As can be seen from Figure 4 it that after adding nanoparticles, the toughness is very high. No cracks are generated in the Vickers hardness indentation. (Generally, for brittle materials, cracks will be generated in the Vickers indentation)

[0049] Example 5 TiB2 nanoparticle-reinforced Si-Mg-Al-Zr-Y-B glass-ceramics

[0050] 1. Add 39 g of SiO2 powder, 11 g of MgO powder, 27 g of Al2O3 powder, 9 g of ZrO2 powder, 7 g of Y2O3 powder, 20 g of TiB2 nanoparticles, and 10 g of B2O3 powder into absolute ethanol and ultrasonically disperse for 10 min; then put it into a grinding ball mill and mill for 2 h with a ball-to-material ratio of 1:2 to obtain a uniformly mixed slurry; put the ball-milled slurry into a rotary evaporator, dry it at 80 °C and then pass through a 60-mesh sieve to obtain a mixed powder;

[0051] 2. Dry press the mixed powder using a steel mold at a pressure of 30 MPa to obtain a block of the corresponding shape, and then perform cold isostatic pressing at a pressure of 200 MPa to obtain a green body;

[0052] 3. Use the suspension method to heat the green body to the molten state at 1700 °C, and then perform a cooling treatment at a cooling rate of 250 K / s to obtain TiB2 nanoparticle-reinforced Si-Mg-Al-Zr-Y-B glass-ceramics.

[0053] Comparative Example 1 Y-Al glass-ceramics

[0054] 1. Add 44 g of Y2O3 powder and 56 g of Al2O3 powder into absolute ethanol and ultrasonically disperse for 10 min; then put it into a grinding ball mill and mill for 2 h with a ball-to-material ratio of 1:2 to obtain a uniformly mixed slurry; put the slurry into a rotary evaporator, dry it at 80 °C and then pass through a 60-mesh sieve to obtain a mixed powder;

[0055] 2. Dry press the mixed powder using a steel mold at a pressure of 30 MPa to obtain a block of the corresponding shape, and then perform cold isostatic pressing at a pressure of 200 MPa to obtain a green body;

[0056] 3. The green body is heated to the molten state at 2100 °C by a suspension method and then cooled at a cooling rate of 250 K / s to obtain Y-Al glass ceramics.

[0057] The nano-particle reinforced glass ceramics prepared in Examples 1-5 were subjected to the following property tests: (1) The elastic modulus was measured by a nano-indentation instrument; (2) The toughness test was carried out by an indentation method with a test pressure of 1 kg and a pressure holding time of 10 s. (3) The Vickers hardness was measured by a Vickers hardness tester with a test pressure of 5 kg and a pressure holding time of 10 s. (4) The maximum transmittance in the visible light range of 400-800 nm was measured by an ultraviolet-visible spectrophotometer. (5) The fracture mode was realized by an in-situ micro-column compression experiment.

[0058] Table 1 Properties of the nano-particle reinforced glass ceramics prepared in Comparative Example 1 and Examples 1-5

[0059]

[0060] Table 1 shows the properties of the nano-particle reinforced glass ceramics prepared in Comparative Example 1 and Examples 1-5. It can be seen from Table 1 that the Y-Al glass ceramics in Comparative Example 1 have a relatively high hardness and elastic modulus, but very low toughness, poor wear resistance, brittle fracture, and poor drop resistance. The nano-particle reinforced glass ceramics prepared in Examples 1-5 have adjustable hardness, high toughness, good wear resistance, and pseudo-plastic fracture, and good drop resistance. It can be seen that the nano-particle reinforced glass ceramics of the present invention have high toughness, high hardness, high wear resistance, etc., especially have the characteristics of pseudo-plastic fracture and adjustable transparency, and have great application value in intelligent devices, ultra-high temperature glass and precision instruments.

[0061] The above embodiments are the preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and shall be included in the protection scope of the present invention.

Claims

1. A nanoparticle-reinforced glass-ceramic, characterized in that, The nano-particle reinforced glass-ceramic is obtained by pressing a mixed powder of oxide powder, nano-particles and low-temperature melting aids with a mass ratio of (50-99.5):(0.5-40):(0-15) to obtain a green body; and then heating the green body to a molten state at 1200-2700 °C by a suspension method and cooling it.

2. The nano-particle reinforced glass-ceramic according to claim 1, characterized in that, The mass ratio of the oxide powder, nano-particles and low-temperature melting aids is (75-90):(2-30):(5-10).

3. The nano-particle reinforced glass-ceramic according to claim 1 or 2, characterized in that, The oxide powder is two or more of TiO2, ZrO2, HfO2, MgO, Al2O3, SiO2, Sc2O3, Cr2O3, Re2O3.

4. The nanoparticle-reinforced glass ceramic according to claim 3, wherein The Re2O3 is Y2O3, La2O3, Ce2O3 or Sm2O 3。 5. The nanoparticle-reinforced glass-ceramic according to claim 1 or 2, wherein The nano-particles are one or more of TiN, TiC, Ti(C,N), ZrB2, TiB2, WC, SiC, TaC, TaN or Si3N4.

6. The nanoparticle-reinforced glass ceramic according to claim 1 or 2, characterized in that, The low-temperature melting aids are B2O3, CaO, BaO, Na2O, K2O, P2O5, Li2O, SrO, ZnO or PbO.

7. The nanoparticle-reinforced glass ceramic according to claim 1, characterized in that, The hardness of the described nanoparticle-reinforced glass-ceramics is ≥8 GPa, and the toughness is ≥6 MPa·m 1 / 2 and the maximum transmittance in the visible light range is 84%.

8. The preparation method of the 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, nano-particles and low-temperature melting aids to obtain a mixed powder; S2. Perform cold isostatic pressing on the mixed powder at a pressure of 100-200 MPa to form a green body; S3. Heat the green body to a molten state at 1200-2700 °C by a suspension method, and then cool it to obtain the nano-particle reinforced glass-ceramic.

9. The preparation method of the nanoparticle-reinforced glass ceramic according to claim 8, wherein, The suspension method described in step S3 is pneumatic suspension, electromagnetic suspension or electrostatic suspension.

10. Application of the nano-particle reinforced glass-ceramic according to any one of claims 1-7 in intelligent devices, ultra-high temperature glass or precision instruments.

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