High-toughness composite glass substrates, methods of making and using the same

Abstract

The application discloses a high-toughness composite glass substrate and a preparation method and application thereof. The composite glass substrate comprises a glass base and metal particles; the mass fraction of the metal particles is 1-20%; the metal particles comprise metal particles with two or more parameter specifications, the parameter specifications comprising a specific surface area parameter and an oxidation activity parameter. According to the embodiment of the application, oxidation of the metal additive can be avoided, and the toughness of the glass is improved.

Description

High-toughness composite glass substrates, their preparation methods and applications Technical Field

[0001] This application belongs to the field of glass materials, and in particular relates to a high-toughness composite glass substrate, its preparation method and application. Background Technology

[0002] Glass is an amorphous inorganic non-metallic material, generally made from a variety of inorganic minerals, such as quartz sand, borax, boric acid, barite, barium carbonate, limestone, feldspar and soda ash, as the main raw materials, with the addition of a small amount of auxiliary materials.

[0003] Glass is a hard-brittle material, meaning it has high hardness but low toughness. Therefore, its toughness is the biggest limiting factor in its applications. For example, when glass is used as a sealing material for electrical penetrations in high-temperature gas-cooled reactors, brittle fracture is the primary failure mode, leading to crack initiation and propagation. Furthermore, if cracks connect, gas leakage can occur, reducing the lifespan and reliability of the electrical penetrations. Therefore, increasing the toughness of glass is essential for its use as a structural material. Summary of the Invention

[0004] This application provides a high-toughness composite glass substrate, its preparation method, and its application, which can avoid oxidation of metal additives and improve the toughness of glass.

[0005] In the first aspect, embodiments of this application provide a high-toughness composite glass substrate, which includes a glass matrix and metal particles; the mass fraction of the metal particles is 1%-20%; the metal particles include metal particles with two or more parameter specifications, including specific surface area parameter and oxidation activity parameter.

[0006] In any embodiment of this application, the metal particles include first metal particles and second metal particles; wherein the specific surface area of ​​the first metal particles is 0.1-1 m². 2 / g; the specific surface area of ​​the second metal particle is 1-10m². 2 / g; the oxidation activity of the first metal particle is less than that of the second metal particle; the mass fraction of the first metal particle is greater than that of the second metal particle.

[0007] In any embodiment of this application, the particle size of the first metal particle is 1-10 μm, and the particle size of the second metal particle is 0.1-0.8 μm.

[0008] In any embodiment of this application, the volume ratio of a single first metal particle to a single second metal particle is 100-1000:1.

[0009] In any embodiment of this application, the mass fraction of the first metal particle is 3%-20%, and the mass fraction of the second metal particle is 1%-10%.

[0010] In any embodiment of this application, the first metal particle comprises at least one of aluminum, silver, platinum and gold, or an alloy thereof.

[0011] In any embodiment of this application, the second metal particle comprises at least one of chromium, iron, zinc and nickel, or an alloy thereof.

[0012] In any embodiment of this application, the surface of the first metal particle is passivated, and the surface of the second metal particle is activated.

[0013] In any embodiment of this application, the fracture toughness of the composite glass substrate is 1-3 MPa·m. 0.5 .

[0014] Secondly, embodiments of this application provide a method for preparing a composite glass substrate, comprising: sintering and melting a raw material containing a glass matrix and metal particles, followed by cooling and solidification to obtain a composite glass substrate; wherein the metal particles include metal particles with two or more parameter specifications, the parameter specifications including specific surface area parameter and oxidation activity parameter.

[0015] Thirdly, embodiments of this application provide the application of the above-described composite glass substrate or the composite glass substrate obtained by the above-described preparation method in solid oxide fuel cells, solar collector tubes, and electrical penetrations.

[0016] The high-toughness composite glass substrate, its preparation method, and its application in this application improve the toughness of the composite glass substrate by adding metal particles with different oxidation activities, specific surface areas, and mass fractions to the glass matrix. This toughening effect prevents the metal particles from being oxidized. Attached Figure Description

[0017] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments of this application will be briefly introduced below. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 is a schematic diagram of the structure of the composite glass substrate of some embodiments of this application.

[0019] Among them, 1 is a glass matrix; 2 is a second metal particle; and 3 is a first metal particle. Detailed Implementation

[0020] To better understand the above-mentioned objectives, features, and advantages of this application, the solution of this application will be further described below. It should be noted that, unless otherwise specified, the embodiments and features described in these embodiments can be combined with each other.

[0021] Numerous specific details are set forth in the following description in order to provide a full understanding of this disclosure, but this application may also be implemented in other ways different from those described herein; obviously, the embodiments in the specification are only some embodiments of this application, and not all embodiments.

[0022] The high-toughness composite glass substrate of this application, its preparation method, and its application embodiments are disclosed in detail below with appropriate reference to the accompanying drawings. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of actually identical structures may be omitted. This is to avoid making the following description unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided to enable those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.

[0023] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0024] Unless otherwise specified, all embodiments and optional embodiments of this application may be combined with each other to form new technical solutions, and such technical solutions should be considered to be included in the disclosure of this application.

[0025] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions, and such technical solutions shall be deemed to be included in the disclosure of this application.

[0026] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0027] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0028] Unless otherwise specified, this application uses conventional testing methods or testing methods recommended by the instrument.

[0029] Existing technologies employ various methods to enhance glass toughness, such as phase transformation toughening to dissipate fracture energy, and adding ceramic particles to deflect cracks and dissipate fracture energy. Metals are highly tough materials, and adding metal particles to glass to create composite glass substrates can improve their toughness. KR1020210007504A proposes adding metals to glass, utilizing the plastic deformation of the metal to absorb crack propagation energy and improve the fracture toughness of sealed glass composites. JP5880043B2 proposes adding elemental or alloy metal powders to glass, increasing the glass's toughness through the metal's plastic effect and mitigating stress between the sealing layer and the sealed layer. Powder metallurgy is a widely used industrial method for glass manufacturing. In this process, glass sintering typically involves temperatures around 800°C, where metal particles are highly susceptible to oxidation in the sintering atmosphere. Metal oxides may hinder further adhesion between the glass and metal particles, thus impeding stress transfer from the glass matrix to the metal particles, making it difficult for the metal particles to undergo plastic deformation to dissipate fracture energy; furthermore, the areas containing brittle metal oxides are weak areas prone to crack initiation. The oxidation of metals can significantly reduce the toughness of composite glass substrates. Therefore, there is an urgent need for a method to prevent the oxidation of metal additives in composite glass substrates in order to improve the toughness of the glass to a greater extent.

[0030] This application introduces metal particles with different functions into a glass matrix. These particles include those with weak oxidizing activity and large particle size, and those with strong oxidizing activity and small particle size. The large-particle-size metal particles act as toughening agents, while the small-particle-size metal particles compete for oxygen. Due to their different specific surface areas and oxidation activities, the small-particle-size metal particles more readily acquire oxygen, thereby preventing the oxidation of the large-particle-size metal particles that provide toughening and improving the toughness of the composite glass substrate.

[0031] Composite glass substrate

[0032] A high-toughness composite glass substrate, comprising a glass matrix and metal particles; the mass fraction of the metal particles is 1%-20%; the metal particles include metal particles with two or more parameter specifications, including specific surface area parameter and oxidation activity parameter. The mass fraction of the metal particles refers to the percentage of the mass of the metal particles in the composite glass substrate.

[0033] In some embodiments, the metal particles include first metal particles and second metal particles; wherein the specific surface area of ​​the first metal particles is 0.1-1 m². 2 / g; the specific surface area of ​​the second metal particle is 1-10m². 2 / g; The oxidation activity of the first metal particle is less than that of the second metal particle; The mass fraction of the first metal particle is greater than that of the second metal particle. The mass fraction of the first metal particle refers to the percentage of the mass of the first metal particle in the composite glass substrate. Oxidation activity refers to the ease with which a substance combines with an oxidizing agent. Because the oxidation activity of the first metal particle is less than that of the second metal particle, during the sintering process of the glass, the second metal particle will compete for more oxygen and undergo oxidation, but due to its small mass fraction, its impact on the performance of the composite material is limited; while the oxidation of the second metal particle will protect the first metal particle from oxidation, thus allowing the first metal particle to play a better toughening role. As shown in Figure 1, the uniform dispersion of the first and second metal particles in the glass matrix can improve the toughness of the glass.

[0034] In some embodiments, the particle size of the first metal particle is 1-10 μm, and the particle size of the second metal particle is 0.1-0.8 μm. Optionally, the particle size of the first metal particle is 5 μm, and the particle size of the second metal particle is 0.5 μm. Particle sizes within this range will cause significant stress fluctuations in the first metal particle within the composite material, having a greater impact on the composite material's performance; while the impact of the second metal particle on the composite material's performance will be smaller. Overall, this results in a composite material with better toughness.

[0035] In some embodiments, the volume ratio of a single first metal particle to a single second metal particle is 100-1000:1. Within this range, the oxidation protection effect of the second metal particle and the toughening effect of the first metal particle are optimally balanced, thereby giving the composite material better toughness.

[0036] In some embodiments, the mass fraction of the first metal particles is 3%-20%, and the mass fraction of the second metal particles is 1%-10%. Optionally, the mass fraction of the first metal particles is 5%-10%, and the mass fraction of the second metal particles is 2%-5%. Within this range, it can play a role in toughening and oxidation protection, while avoiding problems such as excessive porosity and increased glass transition temperature of the composite glass substrate.

[0037] In some embodiments, the first metal particle comprises at least one of aluminum, silver, platinum, and gold, or an alloy thereof. Optionally, the first metal particle is aluminum. Aluminum has a low elastic modulus, is prone to plastic deformation, and has a good effect on absorbing fracture energy. After oxidation, a dense oxide film (alumina) forms on its surface, preventing further oxidation of elemental aluminum. Furthermore, alumina has good adhesion to the glass matrix, which is beneficial for load transfer between the glass matrix and the reinforcing particles.

[0038] In some embodiments, the second metal particles include at least one of chromium, iron, zinc, and nickel, or an alloy thereof. Optionally, the second metal particles are an iron-nickel alloy, designated 4J42. 4J42 has a coefficient of thermal expansion close to that of glass, thus having a relatively small impact on the mechanical properties of the composite glass substrate. Simultaneously, 4J42 exhibits good adhesion to the glass matrix, and is also readily oxidized. When the second metal particles are chromium, the chromium oxide generated by oxidation readily dissolves and diffuses into the glass matrix, increasing the concentration of homologous oxides in the glass, enhancing the bonding strength between the glass and the metal, and the diffusion of chromium oxide into the glass matrix facilitates the consumption and generation of new chromium oxide.

[0039] In some embodiments, the surface of the first metal particle is passivated, and the surface of the second metal particle is activated. Surface modification can reduce the surface activity of the first metal particle and increase the surface activity of the second metal particle.

[0040] In some embodiments, the fracture toughness of the composite glass substrate is 1-3 MPa·m. 0.5 .

[0041]

Preparation Method

[0042] A method for preparing a composite glass substrate includes: sintering and melting a raw material containing a glass matrix and metal particles, followed by cooling and solidification to obtain the composite glass substrate; wherein the metal particles include two or more types of metal particles with different parameters, including specific surface area and oxidation activity parameters. In the step of sintering and melting the raw material containing the glass matrix and metal particles, the metal particles can be added to the glass raw material powder, mixed evenly, and then sintered together.

[0043]

application

[0044] The composite glass substrate described above, or the composite glass substrate obtained by the above preparation method, is used in solid oxide fuel cells, solar collector tubes, and electrical penetrations. Particularly in electrical penetrations, the high-toughness composite glass substrate can prevent the initiation and propagation of cracks, greatly improving the reliability and service life of the electrical penetrations.

[0045] Example 1

[0046] Step 1: Weigh out 94% of the glass matrix, which is made of TH-3 borosilicate high-temperature sealing glass powder. Then weigh out 5% of the glass matrix, with a specific surface area of ​​0.44 m². 2 / g, Al with a particle size of 5um, weigh out 1% by mass fraction, with a specific surface area of ​​1.48m² 2 / g, 4J42 with a particle size of 0.5um.

[0047] Step 2: Sinter the glass matrix raw material, Al and 4J42 from Step 1 at 800℃ to a molten state, hold at that temperature for 0.5h, then cool to room temperature and solidify to obtain the composite glass substrate.

[0048] Comparative Example 1

[0049] The experimental steps were the same as in Example 1, except that the two metal particles in step 1 were changed to a single Al, and a composite glass substrate was finally obtained.

[0050] Data Analysis:

[0051] The toughness and mechanical strength of the composite glass substrates in Example 1 and Comparative Example 1 were tested using the following methods:

[0052] Fracture toughness: Indentation method; Instrument: Vickers hardness tester; Formula:

[0053] K IC =0.016(E / H) 1 / 2 PC -3 / 2

[0054] Where E is the elastic modulus, H is the hardness, C is the half-length of the indentation crack, and P is the load, all in SI units.

[0055] Compressive strength: Refer to GB / T 4740-1999; Instrument: Universal testing machine.

[0056] The test results are shown in Table 1:

[0057] Serial Number Fracture Toughness (MPa·m) 0.5 Compressive strength (MPa) Example 11.22157 Comparative Example 10.86106 surface

[0058] The above description is merely a specific implementation of this application. Those skilled in the art will clearly understand that, for the sake of convenience and brevity, the specific working processes of the systems, modules, and units described above can be referred to the corresponding processes in the foregoing method embodiments, and will not be repeated here. It should be understood that the protection scope of this application is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in this application, and these modifications or substitutions should all be covered within the protection scope of this application.

Claims

1. A high-toughness composite glass substrate, characterized in that, The composite glass substrate comprises a glass matrix and metal particles; the mass fraction of the metal particles is 1%-20%; the metal particles have two or more parameter specifications, including specific surface area and oxidation activity parameters; the metal particles include first metal particles and second metal particles; wherein the specific surface area of ​​the first metal particles is 0.1-1 m². 2 / g, the specific surface area of ​​the second metal particle is 1-10m² 2 / g, and the specific surface area of ​​the first metal particle is not equal to that of the second metal particle; the oxidation activity of the first metal particle is less than that of the second metal particle; the mass fraction of the first metal particle is greater than that of the second metal particle.

2. The composite glass substrate according to claim 1, characterized in that, The particle size of the first metal particle is 1-10 μm, and the particle size of the second metal particle is 0.1-0.8 μm; and or, the volume ratio of a single particle of the first metal particle to that of the second metal particle is 100-1000:

1.

3. The composite glass substrate according to claim 1, characterized in that, The mass fraction of the first metal particle is 3%-20%, and the mass fraction of the second metal particle is 1%-10%.

4. The composite glass substrate according to claim 1, characterized in that, The first metal particle includes at least one of aluminum, silver, platinum and gold, or an alloy thereof.

5. The composite glass substrate according to claim 1, characterized in that, The second metal particle includes at least one of chromium, iron, zinc and nickel, or an alloy thereof.

6. The composite glass substrate according to claim 1, characterized in that, The surface of the first metal particle is passivated, and the surface of the second metal particle is activated.

7. The composite glass substrate according to claim 1, characterized in that, The fracture toughness of the composite glass substrate is 1-3 MPa·m. 0.5 .

8. A method for preparing a composite glass substrate, characterized in that, include: The composite glass substrate is obtained by sintering and melting a raw material containing a glass matrix and metal particles, followed by cooling and solidification. The metal particles have two or more parameter specifications, including specific surface area and oxidation activity. The metal particles include first metal particles and second metal particles. The specific surface area of ​​the first metal particles is 0.1-1 m². 2 / g, the specific surface area of ​​the second metal particle is 1-10 m² / g. 2 / g, and the specific surface area of ​​the first metal particle is not equal to that of the second metal particle; the oxidation activity of the first metal particle is less than that of the second metal particle; the mass fraction of the first metal particle is greater than that of the second metal particle.

9. The application of the composite glass substrate according to any one of claims 1-7 or the composite glass substrate obtained by the preparation method according to claim 8 in solid oxide fuel cells, solar collector tubes and electrical penetrations.

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