Multifunctional nano-loaded porous micro aggregate, and preparation method and application thereof

Abstract

This invention discloses a multifunctional nano-loaded porous microaggregate, its preparation method, and its applications. The multifunctional nano-loaded porous microaggregate includes modified carbonate particles and nanofunctional materials loaded on the modified carbonate particles. The modified carbonate particles are obtained by surface roughening and / or porosification of a carbonate matrix material. This application uses widely available carbonate materials and employs a low-energy-consumption rapid calcination technology to porosilicate / roughen the surface of the carbonate materials, which is more conducive to the loading of nanofunctional materials. Further heat treatment further enhances the loading degree between the nanofunctional materials and the modified carbonate materials. This method is suitable for large-scale production, has low cost, and yields materials with good electrical conductivity and mechanical properties, making it suitable for various construction fields.

Description

Technical Field

[0001] This invention relates to the field of building materials technology, and in particular to a multifunctional nano-loaded porous micro-aggregate, its preparation method, and its application. Background Technology

[0002] Concrete is one of the most widely used building materials globally, but the performance limitations of traditional concrete restrict its potential in various applications. One of the key components of concrete is aggregate, including fine and coarse aggregates, which account for over 60% of the concrete volume. Typical sand and gravel aggregates and manufactured sand often have a dense structure and smooth surface, limiting the versatility of concrete. Aggregates play a crucial role in concrete, but their function is singular, including providing mechanical support and filling, while also being a weak point for concrete performance degradation. To meet the diverse performance requirements of modern society for concrete materials, there is an urgent need for new materials and preparation methods to achieve the functional transformation of concrete.

[0003] Meanwhile, commonly used nanostructured porous materials, such as molecular sieves and MOF (metal-organic framework) nanomaterials, exhibit good loading performance, but their synthesis scale is usually limited, making it difficult to meet the needs of large-scale application in building materials such as concrete. Their synthesis processes are complex and costly, and they cannot effectively address the conductivity and strength requirements of large-scale construction projects.

[0004] Therefore, it is essential to provide a nano-loaded porous material with good electrical conductivity and mechanical properties. Summary of the Invention

[0005] In view of this, this application provides a multifunctional nano-loaded porous microaggregate, its preparation method and application, to solve the problem of how to improve the electrical conductivity and mechanical properties of building materials.

[0006] To achieve the above technical objectives, this application adopts the following technical solution:

[0007] In a first aspect, this application provides a multifunctional nano-loaded porous microaggregate, comprising modified carbonate particles and nanofunctional materials loaded on the modified carbonate particles; the modified carbonate particles are obtained by surface roughening and / or porosification of a carbonate matrix material.

[0008] Preferably, the carbonate matrix material includes limestone and / or dolomite.

[0009] Preferably, the nanomaterials include one or more of graphene, carbon nanotubes, and silver nanoparticles.

[0010] Preferably, the particle size of the nanofunctional material is 10-20 nm.

[0011] Preferably, the particle size of the carbonate matrix material is 20-50µm.

[0012] Secondly, this application provides a method for preparing multifunctional nano-supported porous microaggregates, comprising the following steps:

[0013] S1. Calcine the carbonate matrix material to obtain modified carbonate particles;

[0014] S2. Using an impregnation method, nanofunctional materials are loaded onto modified carbonate particles to obtain a porous micro-aggregate precursor;

[0015] S3. Heat-treated porous micro-aggregate precursor, namely multifunctional nano-loaded porous micro-aggregate.

[0016] Preferably, in step S1, the calcination temperature is 600-900℃ and the calcination time is 2-4h.

[0017] Preferably, in step S2, the mass ratio of the nanofunctional material to the carbonate matrix material is 5-8:100.

[0018] Preferably, in step S3, the heat treatment temperature is 100-200℃ and the heat treatment time is 1-3h.

[0019] Thirdly, this application provides an application of multifunctional nano-loaded porous micro-aggregates in building materials.

[0020] The beneficial effects of this application are as follows: This application uses widely available carbonate materials and low-energy rapid calcination technology to make the surface of the carbonate materials porous / rough, which is conducive to the loading of nano-functional materials. Then, through heat treatment, the loading degree of nano-functional materials and modified carbonate materials is further enhanced. This solution is suitable for large-scale production, has low cost, and the obtained materials have good electrical conductivity and mechanical properties, making them suitable for various construction fields. Attached Figure Description

[0021] Figure 1 Here is an electron micrograph of the modified carbonate particles obtained in Example 1;

[0022] Figure 2 Here is an electron micrograph of the modified carbonate particles obtained in Example 2;

[0023] Figure 3 The results of compressive strength tests on different materials;

[0024] Figure 4 These are the resistivity test results for different materials. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0026] In a first aspect, this application provides a multifunctional nano-loaded porous microaggregate, comprising modified carbonate particles and nanofunctional materials loaded on the modified carbonate particles; the modified carbonate particles are obtained by surface roughening and / or porosification of a carbonate matrix material.

[0027] In this application, most (50-90%) of the nanofunctional materials are loaded on the surface of the modified carbonate particles, and a small portion (1-50%) is loaded inside the modified carbonate particles.

[0028] In some embodiments, the carbonate matrix material includes limestone and / or dolomite.

[0029] In some embodiments, the nanomaterials include one or more of graphene, carbon nanotubes, and silver nanoparticles.

[0030] In some embodiments, the particle size of the nanofunctional material is 10-20 nm.

[0031] In some embodiments, the particle size of the carbonate matrix material is 20-50 µm.

[0032] This application provides a method for preparing multifunctional nano-supported porous microaggregates, comprising the following steps:

[0033] S1. Calcine the carbonate matrix material to obtain modified carbonate particles;

[0034] S2. Using an impregnation method, nanofunctional materials are loaded onto modified carbonate particles to obtain a porous micro-aggregate precursor;

[0035] S3. Heat-treated porous micro-aggregate precursor, namely multifunctional nano-loaded porous micro-aggregate.

[0036] In this application, step S1 uses widely available carbonate materials as the matrix material. These materials have a natural porous structure with a porosity of 30-90%, which facilitates subsequent functionalization. After low-temperature calcination, the surface of the carbonate matrix material forms a porous or rough morphology, while the interior remains carbonate material. Steps S2 and S3 involve loading nanofunctional materials into the interior and / or surface of modified carbonate particles through impregnation, mixing, and subsequent heat treatment. This process involves impregnating the carbonate material in a solution containing nanofunctional materials, followed by heat treatment to ensure uniform distribution and good adhesion of the nanomaterials.

[0037] This application utilizes bulk carbonate materials as a matrix and a low-energy, rapid-firing preparation method to achieve the large-scale application of porous materials. Traditional building materials have limited functionality and cannot meet various application needs. This application, by loading nanomaterials and leaving most of the nanomaterials on the matrix surface, endows building materials with certain functional properties, such as conductivity, adsorption, and flame retardancy. These properties broaden the application fields of concrete, such as intelligent sensing, electromagnetic shielding, and pollutant control.

[0038] In some embodiments, in step S1, the calcination temperature is 600-900°C and the calcination time is 2-4 hours. Step S1 also includes cleaning and drying the carbonate matrix material to remove surface impurities.

[0039] In some embodiments, in step S2, the mass ratio of the nanofunctional material to the carbonate matrix material is 5-8:100. The impregnation process involves immersing the modified carbonate particles in a dispersion of the nanofunctional material to ensure sufficient contact and adsorption. During this process, if there is too much nanofunctional material, it will affect the subsequent heat treatment, causing the nanofunctional material to precipitate and not adhere well to the surface of the modified carbonate particles. If there is too little nanofunctional material, the dispersion will be uneven.

[0040] In some embodiments, in step S3, the heat treatment temperature is 100-200°C and the heat treatment time is 1-3 hours.

[0041] Within this limited range, it is beneficial for nanomaterials to be fixed inside and / or on the surface of modified carbonate particles. If the temperature is too low, the moisture cannot be evaporated quickly enough, making it difficult for the nanomaterials to remain on the surface, while if the temperature is too high, it will affect the size of the nanomaterials.

[0042] This application provides the application of a multifunctional nano-loaded porous micro-aggregate in building materials, particularly as an application in conductive concrete and / or flame-retardant concrete.

[0043] This application utilizes readily available carbonate materials as the matrix, which are widely sourced. Conductive concrete is prepared by loading conductive materials such as nano-graphene and carbon nanotubes, achieving a functional transformation of conventional carbonate aggregates. This aggregate not only maintains its fundamental structural role in concrete but also introduces additional functionality, making it suitable for applications such as geothermal systems, smart buildings, and electromagnetic shielding. This provides a broad prospect for the functionalization of concrete materials to meet diverse application and functional requirements.

[0044] The following specific embodiments further illustrate this solution.

[0045] Example 1

[0046] A method for preparing multifunctional nano-supported porous microaggregates includes the following steps:

[0047] S1. Limestone ore with a particle size of 30µm was calcined at 600℃ for 2h to obtain modified carbonate particles with porous surfaces. The electron microscopy results are as follows. Figure 1 As shown, its surface is porous calcium oxide;

[0048] S2. Modified carbonate particles are mixed with ethanol to obtain a suspension. Graphene nanosheets with a particle size of 10 nm are added to the suspension and dispersed by ultrasonication to obtain a porous micro-aggregate precursor, wherein the mass of the graphene nanosheets is 8% of the mass of the limestone.

[0049] The porous micro-aggregate precursor is heated at 105℃ for 2 hours and then dried to firmly load graphene nanosheets onto modified carbonate particles, thus producing a multifunctional nano-loaded porous micro-aggregate.

[0050] Example 2

[0051] A method for preparing multifunctional nano-supported porous microaggregates includes the following steps:

[0052] S1. Dolomite ore with a particle size of 50µm was calcined at 700℃ for 1 hour to form rough magnesium oxide on the surface, thus obtaining modified carbonate particles. The electron microscopy results are as follows: Figure 2 As shown, its surface is rough magnesium oxide;

[0053] S2. Modified carbonate particles are mixed with ethanol at a solid-liquid ratio of 16:100 to obtain a suspension. Carbon nanotubes with a particle size of 10 nm are added to the suspension and dispersed by ultrasonication to obtain a porous micro-aggregate precursor, wherein the mass of carbon nanotubes is 5% of the mass of limestone.

[0054] The porous micro-aggregate precursor is heated at 105℃ for 2 hours and then dried to firmly load graphene nanosheets onto modified carbonate particles, thus producing a multifunctional nano-loaded porous micro-aggregate.

[0055] Example 3

[0056] A method for preparing multifunctional nano-supported porous microaggregates includes the following steps:

[0057] S1. Limestone ore with a particle size of 40µm was calcined at 650℃ for 2h, and then rapidly heated at 900℃ and held for 5 minutes to obtain modified carbonate particles with porous surface.

[0058] S2. Silver nanoparticles with an average diameter of 10-20 nm are dispersed in deionized water containing surfactants, then mixed with modified carbonate particles, and ultrasonically stirred to obtain a porous micro-aggregate precursor.

[0059] S3. The porous micro-aggregate precursor is heated at 200℃ for 1 hour and then dried to obtain multifunctional nano-loaded porous micro-aggregate.

[0060] Example 4

[0061] A method for preparing multifunctional nano-loaded porous microaggregates is described, which is the same as in Example 1 except that graphene nanosheets are replaced with carbon nanotubes.

[0062] Example 5

[0063] A method for preparing multifunctional nano-loaded porous microaggregates is the same as in Example 2, except that carbon nanotubes are replaced with graphene nanosheets.

[0064] Comparative Example 1

[0065] A method for preparing multifunctional nano-loaded porous micro-aggregates is the same as in Example 1, except that steps S2 and S3 are not included, i.e., porous calcium oxide is obtained.

[0066] Comparative Example 2

[0067] A method for preparing multifunctional nano-loaded porous micro-aggregates is the same as in Example 2, except that steps S2 and S3 are not included, thus obtaining rough magnesium oxide.

[0068] Testing and Evaluation

[0069] The multifunctional nano-loaded porous micro-aggregates obtained in Examples 1, 4, and Comparative Example 1 were used as aggregates to prepare mortars, while the multifunctional nano-loaded porous micro-aggregates obtained in Examples 2, 5, and Comparative Example 2 were used as aggregates to prepare mortars. After each mortar cured, its compressive strength and resistivity were tested. The results are as follows: Figure 3 , Figure 4 As shown in the figure. Examples 1 and 4 correspond to the results of loaded carbon nanotubes and loaded graphene, respectively, while Examples 2 and 5 correspond to the results of loaded graphene and loaded carbon nanotubes, respectively.

[0070] This application utilizes widely available carbonate materials and employs a low-energy, rapid calcination technique to porousen / roughen the surface of the carbonate materials, which is more conducive to the loading of nanofunctional materials. Further heat treatment enhances the loading of nanofunctional materials and modified carbonate materials. This solution is suitable for large-scale production, has low cost, and produces materials with good electrical conductivity and mechanical properties, making it suitable for various construction fields.

[0071] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing multifunctional nano-supported porous microaggregates, characterized in that, Includes the following steps: S1. Calcine the carbonate matrix material to obtain modified carbonate particles; S2. Using an impregnation method, nanofunctional materials are loaded onto the modified carbonate particles to obtain a porous micro-aggregate precursor; S3. Heat-treat the porous micro-aggregate precursor to obtain the multifunctional nano-supported porous micro-aggregate; the carbonate matrix material includes limestone and / or dolomite; in step S1, the calcination temperature is 600-900℃ and the calcination time is 2-4h; in step S3, the heat treatment temperature is 100-200℃ and the heat treatment time is 1-3h.

2. The method for preparing multifunctional nano-supported porous microaggregates according to claim 1, characterized in that, In step S2, the mass ratio of the nanofunctional material to the carbonate matrix material is 5-8:

100.

3. A multifunctional nano-loaded porous microaggregate obtained by the preparation method according to any one of claims 1-2, comprising modified carbonate particles and nanofunctional materials loaded on the modified carbonate particles; wherein the modified carbonate particles are obtained by surface roughening and / or porosification of a carbonate matrix material.

4. The multifunctional nano-supported porous microaggregate according to claim 3, characterized in that, The particle size of the nanomaterial is 10-20 nm.

5. The multifunctional nano-supported porous microaggregate according to claim 3, characterized in that, The particle size of the carbonate matrix material is 20-50µm.

6. The application of a multifunctional nano-loaded porous micro-aggregate obtained by the preparation method according to any one of claims 1-2 in building materials.

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