A modified glass powder

Abstract

The application provides a modified glass powder, wherein the surface of the modified glass powder is covered with a dense crystal layer, and the dense crystal layer is Al a K b Ca c Mg d Si e C f O g composite crystal. The glass powder can be added as a filler in various materials, but the current glass itself has high resistivity, so that the application scene is limited. The application modifies the glass powder, so that a dense crystalline layer is formed on the surface of the glass powder, the resistance of the glass powder is reduced, and the performance of the glass powder is improved.

Description

Technical Field

[0001] This invention relates to a modified glass powder, belonging to the field of chemical materials. Background Technology

[0002] Glass is an inorganic non-metallic material primarily composed of silicon dioxide. It is produced by high-temperature melting of ores (pyrophyllite, quartz sand, etc.), and the finished glass itself possesses good corrosion resistance and is stable to most acids, salts, and solvents (except concentrated alkalis and hydrofluoric acid). Glass can be pulverized to form glass powder, which can then be added as a filler to various materials. However, the high resistivity of glass currently limits its application scenarios. Summary of the Invention

[0003] The present invention aims to solve at least one of the technical problems existing in the prior art.

[0004] Therefore, the present invention provides a modified glass powder, wherein the surface of the modified glass powder is covered with a uniform dense crystalline layer, wherein the dense crystalline layer is Al. a K b Ca c Mg d Si e C f O g Composite crystal layer.

[0005] Furthermore, the glass powder has a size of 5μm-4000μm.

[0006] Furthermore, the lattice spacing of the dense crystal layer is 0.1-1 nm.

[0007] Furthermore, the Al a K b Ca c Mg d Si e C f O g The composite crystal has a C molar content of 0-5%, a Si molar content of 10-20%, an Al molar content of 5-20%, a K molar content of 5-12%, a Ca molar content of 0.1-0.5%, and a Mg content of 3-7%.

[0008] Furthermore, the modified glass powder also includes a second composite material layer on its inner side. The second composite material layer is a carbon-silicate composite layer, and the carbon molar content of the second composite material layer is higher than that of the dense crystalline layer.

[0009] Furthermore, the modified glass powder also includes a third composite material layer on its inner side. The third composite material layer is a carbon-silicate composite layer, and the carbon molar content of the third composite material layer is higher than that of the second composite material layer.

[0010] Furthermore, the method for preparing the modified glass powder includes: mixing a carbon source with glass powder and heating it at least once to form at least one dense carbon layer on the surface of the glass powder, wherein the dense carbon layer contains silicates and the carbon source contains potassium, calcium and magnesium elements.

[0011] Furthermore, specifically including:

[0012] S1. Take a carbon source and mix it with glass powder, and heat it to a first temperature to form a first carbon layer on the surface of the glass powder, wherein the first carbon layer contains silicates;

[0013] S2. The material obtained in S1 is heated to a second temperature until the first carbon layer is at least partially converted into the second carbon layer, thereby obtaining a strengthened glass powder, wherein the carbon content of the second carbon layer is higher than that of the first carbon layer S1.

[0014] Furthermore, S1 specifically includes:

[0015] The carbon source and glass powder were mixed at a mass ratio of (0.5-2):(0.1-3) and heated in an oxygen-free environment to form a first carbon layer on the surface of the glass powder, followed by rapid cooling.

[0016] The oxygen-free environment is specifically a nitrogen atmosphere.

[0017] Furthermore, S2 specifically includes:

[0018] Heating in an oxygen-containing environment until the first carbon layer is at least partially transformed into a dense crystalline layer, followed by rapid cooling, yields strengthened glass powder.

[0019] Compared with the prior art, the present invention modifies the glass powder to form a dense crystalline layer on the surface of the glass powder, thereby reducing the resistance of the glass powder and improving its performance. Attached Figure Description

[0020] Figure 1 This is a SEM image of glass powder from an embodiment of the present invention;

[0021] Figure 2 This is a TEM image of a crystal on a dense crystal layer according to an embodiment of the present invention;

[0022] Figure 3 XRD pattern of an embodiment of the present invention;

[0023] Figure 4These are TG-DSC images of the present invention before and after modification (Example 1);

[0024] Figure 5 These are resistance diagrams of the present invention before and after modification (Example 1). Detailed Implementation

[0025] To enable those skilled in the art to better understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0026] This invention discloses a modified glass powder, the surface of which is covered with a uniform dense crystalline layer, the dense crystalline layer being Al. a K b Ca c Mg d Si e C f O g Composite crystal layer.

[0027] In some optional embodiments, the glass powder size is 5μm-4000μm.

[0028] In some alternative embodiments, the lattice spacing of the dense crystal layer is 0.1-1 nm.

[0029] In some alternative embodiments, the Al a K b Ca c Mg d Si e C f O g The composite crystal has a C molar content of 0-5%, a Si molar content of 10-20%, an Al molar content of 5-20%, a K molar content of 5-12%, a Ca molar content of 0.1-0.5%, and a Mg content of 3-7%.

[0030] Optionally, the modified glass powder further includes a second composite material layer, which is a carbon-silicate composite layer, and the carbon molar content of the second composite material layer is higher than that of the dense crystalline layer.

[0031] In some optional embodiments, the modified glass powder further includes a third composite material layer, which is a carbon-silicate composite layer, and the carbon molar content of the third composite material layer is higher than that of the second composite material layer.

[0032] This invention also discloses a method for preparing modified glass powder, comprising:

[0033] S1. Take carbon source and glass powder and mix them in a mass ratio of (0.5-2):(0.1-3), and heat them to the first temperature in an oxygen-free environment to form a first carbon layer on the surface of the glass powder, and then cool them down rapidly.

[0034] S2. Heating to a second temperature in an oxygen-containing environment until the first carbon layer is at least partially converted into a second carbon layer, the second carbon layer being a dense carbon layer, and the carbon molar content of the second carbon layer being higher than that of the first carbon layer.

[0035] In some optional embodiments, S2 specifically includes:

[0036] Heating in an oxygen-containing environment until at least part of the first carbon layer is converted into a dense crystalline layer, followed by rapid cooling, yields recycled glass powder. The oxygen-containing environment can be an air atmosphere, which can be a closed environment or an airflow environment, with an airflow rate of 50-200 ml / min.

[0037] In some optional embodiments, the heating temperature of S1 is the softening temperature of the glass, which is between 500-1200°C. In the embodiments of this application, it is preferably between 500-900°C.

[0038] In some alternative embodiments, the first temperature is higher than the second temperature, and the difference between the first temperature and the second temperature does not exceed 300°C.

[0039] In some optional embodiments, the oxygen-free environment is specifically a nitrogen atmosphere. The nitrogen atmosphere can be a closed nitrogen environment or flowing nitrogen. When the nitrogen atmosphere is flowing nitrogen, the nitrogen flow rate can be 50-200 ml / min. Other inert gases, such as helium, neon, argon, krypton, and xenon, can also be used. It should be noted that the oxygen-free gas referred to in the embodiments of this application is a gas that does not contain oxygen or has an extremely low oxygen molar content.

[0040] In some alternative embodiments, the glass powder is waste wind turbine blades.

[0041] In some alternative embodiments, the waste wind turbine blades are specifically epoxy resin glass powder composite materials.

[0042] In some optional embodiments, the carbon source is at least one of plant-derived biomass and animal-derived biomass.

[0043] In some optional embodiments, the carbon source is plant-derived biomass, which may be selected from herbaceous plant-derived biomass or woody plant-derived biomass. Herbaceous plant-derived biomass may include biomass such as corn cobs.

[0044] In some optional embodiments, the plant-derived biomass contains cellulose fibers, potassium, and calcium. Preferably, the molar content of potassium and calcium in the plant-derived biomass is 2% or more. The cellulose fibers include at least one of lignin, cellulose, and hemicellulose.

[0045] Example 1

[0046] The collected corn cobs were rinsed with deionized water to remove surface impurities and dehydrated in an 80℃ forced-air drying oven for 12 hours. After crushing using a plant pulverizer, the corn cobs were passed through a 20-mesh sieve and stored in a sealed nitrogen atmosphere for later use. Glass powder with a size of 100μm-4000μm was vacuum dried at 105℃ for 24 hours.

[0047] Corn cobs and glass powder were mixed at a mass ratio of 1:1 and placed in a fixed-bed reactor. After nitrogen was introduced to purge the air, the temperature was raised to 600℃ and pyrolyzed at a constant temperature for 60 min under a nitrogen flow of 100 mL / min.

[0048] After the reactor was rapidly cooled to room temperature (5 min), the sample was removed and ultrasonically cleaned with anhydrous ethanol to remove the loose carbon layer on the surface. Finally, it was dried at 80 °C for 12 h under nitrogen protection. The sample formed, from the inside out, a crystalline silicate layer (second composite material layer), a crystalline carbon / silicate composite layer (third composite material layer), a dense crystalline layer, and an amorphous carbon layer (fourth composite material layer).

[0049] The atmosphere was then switched to air, the flow rate was 100 mL / min, and the temperature was raised to 550 °C and held for 30 min. The sample was then removed, and from the inside out, the sample formed a crystalline silicate layer (second composite material layer), a crystalline carbon / silicate composite layer (third composite material layer), and a dense crystalline layer.

[0050] Example 2

[0051] The collected corn cobs were rinsed with deionized water to remove surface impurities and dehydrated in an 80℃ forced-air drying oven for 12 hours. After being crushed using a plant pulverizer, the cobs were passed through a 20-mesh sieve and stored in a sealed nitrogen environment for later use.

[0052] Corn cobs and alkali-free glass powder were mixed at a mass ratio of 1:1 and placed in a fixed-bed reactor. After nitrogen was introduced to purge the air, the temperature was raised to 600℃ and pyrolyzed at a constant temperature for 60 min under a nitrogen flow of 100 mL / min.

[0053] After the reactor was rapidly cooled to room temperature (5 min), the sample was removed and ultrasonically cleaned with anhydrous ethanol to remove the loose carbon layer on the surface. Finally, it was dried at 80 °C for 12 h under nitrogen protection. The sample formed, from the inside out, a crystalline silicate layer (second composite material layer), a crystalline carbon / silicate composite layer (third composite material layer), a dense crystalline layer, and an amorphous carbon layer (fourth material layer).

[0054] The atmosphere was then switched to air, the flow rate was 100 mL / min, and the temperature was raised to 550 °C and held for 30 min. The sample was then removed and named Co-Newfiber. From the inside out, the sample formed a crystalline silicate layer (second composite material layer), a crystalline carbon / silicate composite layer (third composite material layer), and a dense crystalline layer.

[0055] Example 3

[0056] The collected straw was rinsed with deionized water to remove surface impurities and dehydrated in an 80℃ forced-air drying oven for 12 hours. After being crushed using a plant pulverizer, it was passed through a 20-mesh sieve and stored in a sealed nitrogen environment for later use. The glass powder, with a size of 100μm-4000μm, was vacuum dried at 105℃ for 24 hours.

[0057] Straw and glass powder were mixed at a mass ratio of 1:1 and placed in a fixed-bed reactor. After nitrogen was introduced to purge the air, the temperature was raised to 600℃ and pyrolyzed at a constant temperature for 60 min under a nitrogen flow of 100 mL / min.

[0058] After the reactor was rapidly cooled to room temperature (5 min), the sample was taken out and ultrasonically cleaned with anhydrous ethanol to remove the loose carbon layer on the surface. Finally, it was dried at 80°C for 12 h under nitrogen protection. The sample formed a crystalline silicate layer (second composite material layer), a crystalline carbon / silicate composite layer (third composite material layer), a dense crystalline layer, and an amorphous carbon layer from the inside out.

[0059] The atmosphere was then switched to air, the flow rate was 100 mL / min, and the temperature was raised to 550 °C and held for 30 min. The sample was then removed, and the sample surface showed that, from the inside out, a crystalline silicate layer (second composite material layer), a crystalline carbon / silicate composite layer (third composite material layer), and a dense crystalline layer were formed sequentially.

[0060] Example 4

[0061] The collected pine sawdust was rinsed with deionized water to remove surface impurities and then dehydrated in an 80℃ forced-air drying oven for 12 hours. After being crushed using a plant pulverizer, it was passed through a 20-mesh sieve and stored in a sealed nitrogen atmosphere for later use. Glass powder with a size of 100μm-4000μm was vacuum dried at 105℃ for 24 hours.

[0062] Pine wood chips and glass powder were mixed at a mass ratio of 1:1 and placed in a fixed-bed reactor. After nitrogen was introduced to purge the air, the temperature was raised to 600℃ and pyrolyzed at a constant temperature for 60 min under a nitrogen flow of 100 mL / min.

[0063] After the reactor was rapidly cooled to room temperature (5 min), the sample was taken out and ultrasonically cleaned with anhydrous ethanol to remove the loose carbon layer on the surface. Finally, it was dried at 80°C for 12 h under nitrogen protection. The sample formed a crystalline silicate layer (second composite material layer), a crystalline carbon / silicate composite layer (third composite material layer), a dense crystal layer, and an amorphous carbon layer (fourth material layer) from the inside out.

[0064] The atmosphere was then switched to air, the flow rate was 100 mL / min, and the temperature was raised to 550 °C and held for 30 min. The sample was then removed, and the sample surface showed that, from the inside out, a crystalline silicate layer (second composite material layer), a crystalline carbon / silicate composite layer (third composite material layer), and a crystalline carbon layer (first composite material layer) were formed sequentially.

[0065] Example 5

[0066] The collected coconut shells were rinsed with deionized water to remove surface impurities and dehydrated in an 80℃ forced-air drying oven for 12 hours. After crushing using a plant pulverizer, the shells were passed through a 20-mesh sieve and stored in a sealed nitrogen atmosphere for later use. Glass powder with a size of 100μm-4000μm was vacuum dried at 105℃ for 24 hours.

[0067] Coconut shells and glass powder were mixed at a mass ratio of 1:1 and placed in a fixed-bed reactor. After nitrogen was introduced to purge the air, the temperature was raised to 600℃ and pyrolyzed at a constant temperature for 60 min under a nitrogen flow of 100 mL / min.

[0068] After the reactor was rapidly cooled to room temperature (5 min), the sample was taken out and ultrasonically cleaned with anhydrous ethanol to remove the loose carbon layer on the surface. Finally, it was dried at 80°C for 12 h under nitrogen protection. The sample formed a crystalline silicate layer (second composite material layer), a crystalline carbon / silicate composite layer (third composite material layer), a dense crystal layer, and an amorphous carbon layer (fourth material layer) from the inside out.

[0069] The atmosphere was then switched to air, the flow rate was 100 mL / min, and the temperature was raised to 550 °C and held for 30 min. The sample was then removed, and the sample surface showed that, from the inside out, a crystalline silicate layer (second composite material layer), a crystalline carbon / silicate composite layer (third composite material layer), and a dense crystalline layer were formed sequentially.

[0070] Example 6

[0071] The collected rice husks were rinsed with deionized water to remove surface impurities and dehydrated in an 80℃ forced-air drying oven for 12 hours. After being crushed using a plant pulverizer, the husks were passed through a 20-mesh sieve and stored in a sealed nitrogen atmosphere for later use. Glass powder with a size of 100μm-4000μm was vacuum dried at 105℃ for 24 hours.

[0072] Rice husks and glass powder were mixed at a mass ratio of 1:2 and placed in a fixed-bed reactor. After nitrogen was introduced to purge the air, the temperature was raised to 700℃ and pyrolyzed at a constant temperature for 60 min under a nitrogen flow of 100 mL / min.

[0073] After the reactor was rapidly cooled to room temperature (5 min), the sample was taken out and ultrasonically cleaned with anhydrous ethanol to remove the loose carbon layer on the surface. Finally, it was dried at 80°C for 12 h under nitrogen protection. The sample formed a crystalline silicate layer (second composite material layer), a crystalline carbon / silicate composite layer (third composite material layer), a dense crystal layer, and an amorphous carbon layer (fourth material layer) from the inside out.

[0074] The atmosphere was then switched to air, the flow rate was 100 mL / min, and the temperature was raised to 650 °C and held for 30 min. The sample was then removed, and the sample surface showed that, from the inside out, a crystalline silicate layer (second composite material layer), a crystalline carbon / silicate composite layer (third composite material layer), and a dense crystalline layer were formed sequentially.

[0075] like Figure 1 As shown, the modified glass powder of Example 2 has a uniform dense crystalline layer on its surface, which can be further observed from... Figure 2 As can be seen in (a), it is a TEM image of a crystal in a dense crystal layer, and the lattice size of the crystal surface is 0.336 nm.

[0076] like Figure 3 As shown in the XRD pattern, the modified glass powder has obvious K characteristic peaks, indicating that the present invention can introduce K element into the surface of glass powder.

[0077] like Figure 4 As shown, the glass powder before modification used in Example 2 and the glass powder after modification used in Example 2 were tested. From the TG, DSC and DTG curves, it can be seen that the modified glass powder changes less with increasing heat compared to the glass powder before modification, indicating that the modified glass powder has good antioxidant properties.

[0078] like Figure 5 As shown, resistance performance tests were performed on the glass powder before and after modification. It can be seen that the resistance of the modified glass powder decreased significantly, effectively improving the conductivity of the glass powder.

[0079] In the description of this invention, the term "co-pyrolysis" refers to the simultaneous pyrolysis process of biomass and waste glass powder; "two-phase protection" specifically refers to the synergistic protective structure of the carbon layer and the silicate interface phase. The size parameters (such as 1-4cm fragments, 20-mesh particle size, etc.) allow for ±10% process fluctuations while still ensuring the core protective effect.

[0080] In this embodiment of the invention, the reducing gas generated by biomass pyrolysis is used to inhibit the oxidation of the glass powder surface. At the same time, the K / Ca / Mg elements in the ash react with SiO2 on the fiber surface to generate a silicate interface phase, forming a "carbon layer-silicate dual-phase protection" structure, which significantly improves the oxidation resistance and mechanical properties of the glass powder.

[0081] Furthermore, Examples 1-6 of this invention use agricultural waste as co-pyrolysis raw material, which is inexpensive and widely available, achieving the green recycling goal of "treating waste with waste" and is suitable for large-scale industrial applications. This method not only increases the recycling value of glass powder in waste wind turbine blades but also provides a new approach for the efficient recycling of composite materials.

[0082] At the same time, using agricultural waste to achieve "waste treatment with waste" has advantages such as low cost, simple process and environmental friendliness, providing an innovative solution for the high-value recycling of waste wind turbine blades.

[0083] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that after reading this application specification, they can still modify or make equivalent substitutions to the specific implementation of the present invention, but these modifications or changes do not depart from the protection scope of the pending claims of the present invention.

Claims

1. A modified glass powder, characterized in that, The modified glass powder is covered with a uniform dense crystalline layer, which is Al. a K b Ca c Mg d Si e C f O g Composite crystal.

2. The modified glass powder according to claim 1, characterized in that, The glass powder has a size of 5μm-4000μm.

3. The modified glass powder according to claim 1, characterized in that, The lattice spacing of the dense crystal layer is 0.1-1 nm.

4. The modified glass powder according to claim 1, characterized in that, The Al a K b Ca c Mg d Si e C f O g The composite crystal has a C molar content of 0-5%, a Si molar content of 10-20%, an Al molar content of 5-20%, a K molar content of 5-12%, a Ca molar content of 0.1-0.5%, and a Mg content of 3-7%.

5. The modified glass powder according to claim 1, characterized in that, The modified glass powder also includes a second composite material layer inside, which is a carbon-silicate composite layer, and the carbon molar content of the second composite material layer is higher than that of the dense crystal layer.

6. The modified glass powder according to claim 5, characterized in that, The modified glass powder also includes a third composite material layer inside, which is located between the second composite material layer and the dense crystalline layer. The third composite material layer is a carbon-silicate composite layer, and the carbon molar content of the third composite material layer is higher than that of the second composite material layer.

7. The modified glass powder according to claim 1, characterized in that, The method for preparing the modified glass powder includes: mixing a carbon source with glass powder and heating it at least once to form at least one dense carbon layer on the surface of the glass powder, wherein the dense carbon layer contains silicates and the carbon source contains potassium, calcium and magnesium elements.

8. The modified glass powder according to claim 7, characterized in that, Specifically, it includes: S1. Take a carbon source and mix it with glass powder, and heat it to a first temperature to form a first carbon layer on the surface of the glass powder, wherein the first carbon layer contains silicates; S2. The material obtained in S1 is heated to a second temperature until the first carbon layer is at least partially converted into the second carbon layer, thereby obtaining a strengthened glass powder, wherein the carbon content of the second carbon layer is higher than that of the first carbon layer S1.

9. The modified glass powder according to claim 8, characterized in that, S1 specifically includes: The carbon source and glass powder were mixed at a mass ratio of (0.5-2):(0.1-3) and heated in an oxygen-free environment to form a first carbon layer on the surface of the glass powder, followed by rapid cooling. The oxygen-free environment is specifically a nitrogen atmosphere.

10. The modified glass powder according to claim 9, characterized in that, S2 specifically includes: Heating in an oxygen-containing environment until the first carbon layer is at least partially transformed into a dense crystalline layer, followed by rapid cooling, yields strengthened glass powder.

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