Inorganic decorative whole-body aggregate material as well as preparation method and application thereof

Abstract

The invention provides an inorganic decorative whole-body aggregate material as well as a preparation method and application thereof, and belongs to the technical field of building coatings. The inorganic decorative whole-body aggregate material comprises the following components in parts by mass: 35-50 parts of a composite cementing material; 3-7 parts of a composite alkali activator; 45-60 parts of a functional composite filler; 2-6 parts of a crystallization active agent; 1.5 to 4.0 parts of polymer rubber powder; 0.5 to 1.5 parts of a hydrophobic water reducing agent; 0.1 to 0.5 part of a water-retaining agent; wherein the functional composite filler comprises a pigment and a heat-insulating filler; the crystallization active agent comprises a composite structure which takes metakaolin as a core and takes a crystallization type waterproof agent and a nano nucleating agent as a shell. Through a reasonable raw material formula and a unique preparation process, the impermeability, compressive strength and self-repairing performance of the material can be remarkably improved, and the heat conductivity coefficient of the material is reduced.

Description

Technical Field

[0001] This application relates to the field of architectural coatings technology, and in particular to an inorganic decorative solid aggregate material and its preparation method and application. Background Technology

[0002] The traditional process for applying exterior wall marble-look coatings (water-based multicolor) generally involves: leveling and priming with a putty layer, then applying a multicolor intermediate coat, and finally spraying on water-based multicolor dots. This process often has the following drawbacks: 1. Putty, as a base layer leveling and priming material, is often overlooked in terms of quality, leading to various problems in the later stages of coating application. Putty is a cement-based material with high rigidity, making it prone to cracking and other issues later on. Especially without sufficient curing, it often exhibits powdering, peeling, cracking, and efflorescence, severely affecting the quality of the coating application.

[0003] 2. The intermediate coating layer used in traditional stone-like paint systems is an emulsion-based system, which is different from the base putty layer (cement-based). This results in poor interlayer adhesion. In particular, when the putty layer is weak, problems such as "mask tape peeling and curling," peeling, and flaking are likely to occur, which seriously affect the quality of the subsequent coating.

[0004] 3. The intermediate coating used in ordinary faux stone paint is a flat coating system, which basically lacks texture. This leads to two problems. First, the smooth surface of the intermediate coating reduces the adhesion of color dots, making it easy for them to fall off due to rain, freezing, or other environmental factors. Second, the faux stone paint system produced by a flat coating system has poor texture, lacks fullness and three-dimensionality, and the aesthetics of the coating no longer meet market demands.

[0005] 4. Ordinary faux stone paint systems have relatively thin coatings, poor impact and damage resistance, and easily expose the underlying putty layer, resulting in uneven coating color and affecting the overall appearance. Moreover, due to the different material systems of the intermediate coat and the putty layer, it is difficult to repair later. In addition, in areas where the paint film is damaged, rainwater seepage can cause problems such as peeling, cracking, and flaking of the surrounding coating.

[0006] Therefore, in view of the problem that existing materials suffer from performance degradation due to microcracks that develop during long-term use and are difficult to repair, this invention provides an inorganic decorative solid aggregate material with complementary performance and synergistic effect. Summary of the Invention

[0007] This application is made in view of the above-mentioned problems, and its purpose is to provide an inorganic decorative solid aggregate material, its preparation method and application.

[0008] Specifically, the first aspect of this application provides an inorganic decorative solid aggregate material, comprising the following components in parts by mass: 35-50 parts of composite cementitious material; 3-7 parts of composite alkali activator; 45-60 parts of functional composite filler; 2-6 parts of crystallizing activator; 1.5-4.0 parts of polymer powder; 0.5-1.5 parts of hydrophobic water-reducing agent; 0.1-0.5 parts of water-retaining agent; The functional composite filler includes pigments and heat-insulating fillers; the crystallizing activator includes a composite structure with metakaolin as the core and crystalline waterproofing agent and nano nucleating agent as the shell.

[0009] Furthermore, the pigment in the functional composite filler is hydrophobically modified rutile titanium dioxide, with an amount of 8-12 parts; the thermal insulation filler is hollow glass microspheres, with an amount of 35-48 parts; and the true density of the hollow glass microspheres is 0.15-0.35 g / cm³. 3 The compressive strength is not less than 10 MPa.

[0010] Furthermore, in the crystallizing activator, the core has a specific surface area of ​​not less than 15000 m². 2 / kg metakaolin; the nano-nucleating agent in the shell is nano-silica, and the mass ratio of the crystalline waterproofing agent to the metakaolin is 1:3~6.

[0011] Furthermore, the preparation method of the crystallizing activator is as follows: (1) Mechanical activation of metakaolin by mixing it at 200-300 rpm; (2) Add silane coupling agent to metakaolin and increase the rotation speed to 600~800 rpm to obtain a mixture; (3) Adjust the rotation speed to 400~500 rpm and spray nano-silica into the mixture; then add crystalline waterproofing agent and continue mixing to coat; (4) Cool and sieve.

[0012] Furthermore, the composite cementitious material includes silicate cement, metakaolin, and granulated blast furnace slag powder; The composite alkali activator comprises solid sodium silicate and carbonate.

[0013] A second aspect of this invention provides a method for preparing an inorganic decorative solid aggregate material, comprising the following steps: S1: The composite cementitious material, the polymer powder and the water-retaining agent are mixed in a first mixture to obtain a basic mixture; S2: The functional composite filler is mixed with the base mixture for a second time; S3: The composite alkali activator, the hydrophobic water-reducing agent, and the core-shell structure crystallizing activator are mixed with the mixture treated in step S2 in a third mixing process to obtain the inorganic decorative solid aggregate material.

[0014] Furthermore, the rotation speed of the first mixing is 400~500 rpm and the time is 5~10 min; the rotation speed of the second mixing is 100~200 rpm and the time is 8~12 min; the rotation speed of the third mixing is 80~120 rpm and the time is 3~8 min.

[0015] A third aspect of the present invention provides an application of the aforementioned inorganic decorative solid aggregate material, wherein the inorganic decorative solid aggregate material is used to prepare an integrated system for building exterior wall insulation and decoration, and / or interior decorative wall surfaces.

[0016] Furthermore, the inorganic decorative aggregate material is mixed with water at a mass ratio of 1:(0.18~0.25) and stirred to form a slurry.

[0017] Furthermore, the stirring includes mixing at a speed of 200-400 rpm for 30-90 seconds, followed by high-speed dispersion at a speed of 800-1100 rpm for 90-180 seconds; and the slurry is allowed to stand and mature for 5-20 minutes before application.

[0018] The present invention has the following beneficial effects: The inorganic decorative solid aggregate material provided by this invention exhibits excellent performance and a good synergistic effect. From the material itself, the silicate cement, metakaolin, and granulated blast furnace slag powder in the composite cementitious material work together to provide a solid basic structure and strength. The solid sodium silicate and carbonate in the composite alkali activator effectively activate the material, promote the reaction, and improve the material's performance. The rutile titanium dioxide in the functional composite filler imparts good hiding power and weather resistance, while the hollow glass microspheres not only have thermal insulation properties, but their suitable true density and compressive strength ensure the stability and durability of the material during use. The unique core-shell structure of the crystallizing activator, with a specific surface area of ​​not less than 15000 m², provides excellent performance. 2 Using metakaolin as the core and crystalline waterproofing agent and nano-silica as the shell, crystals can be formed inside the material, improving its waterproof performance and impermeability. Polymer powder enhances the material's flexibility and adhesion, while the water-repellent water-reducing agent reduces water consumption and increases density. The water-retaining agent ensures moisture retention during construction, facilitating construction and maximizing material performance. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of this application clearer, the following description and illustration are provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application. All other embodiments obtained by those skilled in the art based on the embodiments provided in this application without inventive effort are within the scope of protection of this application.

[0020] Obviously, the following description is merely some examples or embodiments of this application. Those skilled in the art can apply this application to other similar scenarios without any inventive effort. Furthermore, it is understood that although the effort involved in such development may be complex and lengthy, for those skilled in the art related to the content disclosed in this application, any changes to design, manufacturing, or production based on the technical content disclosed in this application are merely conventional technical means and should not be construed as insufficient disclosure of the content of this application.

[0021] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0022] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0023] An embodiment of the first aspect of this application provides an inorganic decorative solid aggregate material, comprising the following components in parts by mass: 35-50 parts of composite cementitious material; 3-7 parts of composite alkali activator; 45-60 parts of functional composite filler; 2-6 parts of crystallizing activator; 1.5-4.0 parts of polymer powder; 0.5-1.5 parts of hydrophobic water-reducing agent; 0.1-0.5 parts of water-retaining agent; The functional composite filler includes pigments and heat-insulating fillers; the crystallizing activator includes a composite structure with metakaolin as the core and crystalline waterproofing agent and nano nucleating agent as the shell.

[0024] The amount of the composite cementitious material can be any value among 35 parts, 40 parts, 45 parts, and 50 parts. A dosage of less than 35 parts will result in insufficient basic structure and strength of the material, failing to meet the usage requirements; a dosage of more than 50 parts will increase costs and may lead to imbalances in other properties of the material.

[0025] The amount of composite alkali activator can be any value among 3, 4, 5, 6, and 7 parts. If the amount is less than 3 parts, the activity of the material cannot be fully activated, which will affect the improvement of the material's performance. If the amount is more than 7 parts, it may cause excessive reaction, which will lead to a decrease in the stability of the material.

[0026] The amount of functional composite filler can be any value among 45 parts, 50 parts, 55 parts, and 60 parts. If the amount is less than 45 parts, the hiding power of the pigment and the heat insulation effect of the heat insulation filler will be affected; if the amount is more than 60 parts, other properties of the material will be suppressed.

[0027] The amount of crystallizing activator can be any value among 2, 3, 4, 5, and 6 parts. If the amount is less than 2 parts, the improvement in the waterproof performance and impermeability of the material is not obvious; if the amount is more than 6 parts, it may lead to excessive crystallization inside the material, affecting the overall performance of the material.

[0028] The polymer powder is VINNAPAS® 5044N redispersible latex powder, and its dosage is any value among 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, and 4 parts. If the dosage is less than 1.5 parts, the material will lack flexibility and adhesion; if the dosage is more than 4 parts, it will increase the cost and may deteriorate some properties of the material.

[0029] The water-repellent water-reducing agent is a water-repellent polycarboxylate water-reducing agent. Its dosage is any value among 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, and 1.5 parts. If the dosage is less than 0.5 parts, it cannot effectively reduce the water consumption of the material; if the dosage is more than 1.5 parts, it may have a negative impact on other properties of the material.

[0030] The water-retaining agent is hydroxypropyl methylcellulose ether (HPMC, viscosity 40000 mPa·s), and its dosage is any value among 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, and 0.5 parts. If the dosage is less than 0.1 parts, the moisture retention of the material during construction cannot be guaranteed; if the dosage is more than 0.5 parts, it may affect the drying speed and other properties of the material.

[0031] In practical applications, the dosage of each component needs to be adjusted appropriately according to the specific usage scenario and requirements to achieve optimal performance and effect. For example, in building exterior walls with high waterproofing requirements, the dosage of crystallizing activator can be appropriately increased; in interior decorative walls with high flexibility requirements, the dosage of polymer powder can be appropriately increased. Simultaneously, during the preparation process, the specified mixing speed and time must be strictly followed to ensure that all components are thoroughly and uniformly mixed, thereby guaranteeing the quality and performance of the inorganic decorative aggregate material.

[0032] In this embodiment, the pigment in the functional composite filler is rutile titanium dioxide, and its dosage is 8-12 parts; the heat-insulating filler is hollow glass microspheres, and its dosage is 35-48 parts; and the true density of the hollow glass microspheres is 0.15-0.35 g / cm³. 3 The compressive strength is not less than 10 MPa.

[0033] The rutile titanium dioxide in the functional composite filler is hydrophobically modified rutile titanium dioxide, and the modification method is as follows: (1) Mix 1000g of ordinary titanium dioxide with deionized water in a reactor to prepare a uniformly dispersed slurry (the solid content is usually 300~400 g / L); adjust the pH of the slurry to 9~11 with sodium hydroxide and disperse it fully under high-speed stirring (1000 rpm); add sodium silicate solution (45g sodium silicate dissolved in 500mL water) and aluminum sulfate solution (30g aluminum sulfate dissolved in 500mL water) to the slurry in parallel at 50~60℃ and under continuous stirring, so that the amorphous silica and aluminum oxide produced by hydrolysis are uniformly precipitated on the surface of titanium dioxide particles in the form of hydrated oxides, forming a dense silicon-aluminum composite coating layer; after the coating is completed, filter the slurry and wash it with a large amount of deionized water to completely remove the residual electrolyte; (2) The washed filter cake is slurried again in water. 5g of octyltriethoxysilane is mixed with 150mL of anhydrous ethanol and then 300mL of deionized water is added. The mixture is then slowly added to the slurry and reacted at 60~80℃ with continuous stirring for 1~2 hours. After the reaction is completed, the treated slurry is spray-dried or flash-dried to obtain a dry powder.

[0034] After hydrolysis, the alkoxy group (-OR) at one end of the silane coupling agent undergoes a condensation reaction with the silanol group (-SiOH) on the surface of the inorganic coating layer to form a strong Si-O-Si covalent bond; the long-chain alkyl group (such as octyl) at the other end is arranged outward, giving the titanium dioxide particle surface excellent hydrophobicity.

[0035] Rutile titanium dioxide possesses excellent optical properties and chemical stability. Its high refractive index gives the material good gloss and whiteness, significantly improving the appearance quality of coatings and making building walls look more beautiful and clean. At the same time, its chemical stability ensures that it maintains good performance under different environmental conditions, such as high temperature, high humidity, and ultraviolet radiation, and is not prone to discoloration or chalking, thus extending the service life of the coating.

[0036] Furthermore, rutile titanium dioxide can synergistically interact with hollow glass microspheres. Rutile titanium dioxide can fill the gaps between the microspheres, further improving the material's density and stability. Moreover, during application, rutile titanium dioxide helps improve the material's flowability and plasticity, resulting in smoother application and a more uniform coating.

[0037] In this embodiment, the core of the crystallizing activator has a specific surface area of ​​not less than 15000 m². 2 / kg of metakaolin; the nano-nucleating agent is nano-silica, and the mass ratio of the crystalline waterproofing agent to the metakaolin is 1:3~6. The nano-silica used in this invention is hydrophilic nano-silica A200, purchased from Zhongbei Fine Chemical Co., Ltd.

[0038] The larger specific surface area of ​​metakaolin in the crystalline activator provides more active sites for the reaction, enabling it to bind more effectively with the crystalline waterproofing agent and nano-silica. When the mass ratio of the crystalline waterproofing agent to metakaolin is less than 1:6, the excess metakaolin can prevent the crystalline waterproofing agent from fully covering the metakaolin surface, thus hindering the formation of an effective core-shell structure and affecting the material's waterproofing and impermeability. Conversely, when the mass ratio is greater than 1:3, the excessive amount of crystalline waterproofing agent may cause excessively rapid crystallization within the material, resulting in an unstable crystal structure and hindering the improvement of the material's overall performance.

[0039] Nano-silica plays a crucial role in the shell layer of the crystalline surfactant. Its extremely small particle size and large specific surface area allow it to fill the voids between the crystalline waterproofing agent and metakaolin, enhancing the density of the shell layer. Simultaneously, the active groups on the surface of nano-silica can chemically react with the crystalline waterproofing agent and metakaolin, further improving the stability of the core-shell structure. During material application, nano-silica also promotes the uniform distribution of the crystalline waterproofing agent within the material, resulting in more uniform and dense crystallization, thereby improving the material's waterproofing and impermeability.

[0040] This unique core-shell structured crystallizing agent plays a crucial role in inorganic decorative solid aggregate materials. When the material is mixed with water to form a slurry, the crystallizing agent begins to function. Metakaolin, acting as the core, undergoes a volcanic ash reaction in an alkaline environment, consuming calcium hydroxide and generating cementitious products such as hydrated calcium silicate and hydrated calcium aluminate, further enhancing the material's strength. Meanwhile, the crystalline waterproofing agent in the shell reacts with calcium ions in the material under the influence of moisture, forming insoluble crystalline substances that fill the pores of the material, preventing water penetration. Nano-silica further promotes this process, resulting in more complete and uniform crystallization, thus significantly improving the material's waterproof and impermeable properties.

[0041] The crystalline waterproofing agent used in this invention is Richlam200 penetrating crystalline waterproofing agent, which is available on the market.

[0042] In this embodiment, the preparation method of the crystallizing activator is as follows: (1) Mix the metakaolin in a mixer at 200-300 rpm for mechanical activation, and at the same time start the jacket heating to make the material temperature rise uniformly to 40-50℃; preheating can remove the trace moisture adsorbed by the raw material and improve the reaction activity of subsequent coupling agent treatment. (2) Dilute the silane coupling agent KH~550 with 2 times its mass of anhydrous ethanol, and spray it evenly onto the preheated metakaolin in a stirring state through an atomizing spray gun. The spraying process lasts for 3 to 5 minutes, and the rotation speed is increased to 600 to 800 rpm. After spraying, continue mixing at 45°C for 10 minutes to allow the coupling agent to fully chemically bond with the surface of the metakaolin to obtain a mixture. Active organic functional groups are introduced on the surface of the core layer to provide strong chemical anchoring points for the subsequent shell material to firmly coat the core layer. (3) Adjust the speed to 400~500 rpm, spray hydrophilic nano silica into the mixture, control the feeding time to 5~8 minutes, and after the feeding is completed, continue mixing at 500 rpm for 15 minutes to allow the nano silica to adhere firmly to the core surface through physical adsorption and chemical action (coupling agent in step S2) to form the bottom layer structure of the shell. Maintain the mixer speed at 400-500 rpm, then add the crystalline waterproofing agent and continue mixing for coating. Increase the mixer speed to 800-1000 rpm for high-speed impact coating for 20-30 minutes. Utilize mechanochemical action to tightly embed and coat the crystalline waterproofing agent dry powder particles onto the pre-coated nano-SiO2 core layer surface, forming a complete shell layer. The friction and impact at high speed can make the shell material bond more tightly with the core layer. (4) After coating is completed, turn off the heating, cool the material to room temperature, and pass the final product through a 100-mesh vibrating screen to remove any small amount of agglomerates that may be formed, thus obtaining a core-shell structured crystalline activator with good flowability.

[0043] In this embodiment, the composite cementitious material includes 20-28 parts of silicate cement, 10-14 parts of metakaolin, and 5-8 parts of granulated blast furnace slag powder; the composite alkali activator includes 2-4.5 parts of solid sodium silicate and 1-2.5 parts of carbonate (anhydrous potassium carbonate).

[0044] The silicate cement in the composite cementitious material exhibits high early strength and stable later strength growth. During hydration, it forms numerous hydration products, such as calcium hydroxide and hydrated calcium silicate. These products interweave to form a dense structure, providing fundamental strength support for the inorganic decorative aggregate material. Metakaolin, as an active mineral admixture, can undergo a secondary hydration reaction with the calcium hydroxide produced during cement hydration in an alkaline environment, generating more hydrated calcium silicate and hydrated calcium aluminate, further enhancing the material's strength and durability. Granulated blast furnace slag powder is also a high-quality active admixture that can improve the material's microstructure, enhancing its impermeability, frost resistance, and resistance to chemical attack.

[0045] The solid sodium silicate in the composite alkali activator provides an alkaline environment, promoting the hydration reaction of silicate cement, metakaolin, and granulated blast furnace slag powder, thus accelerating the hardening process of the cementitious materials. The carbonate reacts with calcium ions in the cementitious materials to form calcium carbonate precipitate, which fills the pores of the material and increases its density.

[0046] A second aspect of this invention provides a method for preparing an inorganic decorative solid aggregate material, comprising the following steps: S1: The composite cementitious material, the polymer powder and the water-retaining agent are mixed in a mixer for the first time. The mixing speed is 400~500 rpm and the time is 5~10 min to obtain a basic mixture. S2: The functional composite filler is mixed with the base mixture for a second time at a speed of 100-200 rpm for 8-12 min. S3: The composite alkali activator, the hydrophobic water-reducing agent, and the core-shell structure crystallizing activator are mixed with the mixture treated in step S2 for a third mixing. The rotation speed of the third mixing is 80~120 rpm and the time is 3~8 min, to obtain the inorganic decorative solid aggregate material.

[0047] A third aspect of the present invention provides an application of the aforementioned inorganic decorative solid aggregate material, wherein the inorganic decorative solid aggregate material is used to prepare an integrated system for building exterior wall insulation and decoration, and / or interior decorative wall surfaces.

[0048] In this embodiment, the inorganic decorative aggregate material is mixed with water at a mass ratio of 1:(0.18~0.25) and stirred to form a slurry.

[0049] In this embodiment, the stirring includes mixing at a speed of 200-400 rpm for 30-90 seconds, followed by high-speed dispersion at a speed of 800-1100 rpm for 90-180 seconds; and the slurry is allowed to stand and mature for 5-20 minutes before application.

[0050] Example The following examples describe the disclosure of this invention in more detail. These examples are merely illustrative, as various modifications and variations will be apparent to those skilled in the art within the scope of this disclosure. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are based on weight. Unless otherwise stated, all reagents used in the examples are available commercially or synthesized using conventional methods and are ready for use without further processing. Unless otherwise stated, all instruments used in the examples are available commercially.

[0051] Example 1 An inorganic decorative aggregate material is composed of the following components in parts by weight: 24 parts silicate cement, 12 parts metakaolin, 6.5 parts S95 grade granulated blast furnace slag powder, 3.2 parts solid sodium silicate powder, 1.8 parts anhydrous potassium carbonate, 10 parts hydrophobically modified rutile titanium dioxide, 39.5 parts hollow glass microspheres, 3.5 parts crystallization activator, 2.3 parts redispersible latex powder, 0.9 parts hydrophobic polycarboxylate superplasticizer, and 0.3 parts hydroxypropyl methylcellulose ether.

[0052] The silicate cement was purchased from Jinzhou Baixin Trading Co., Ltd. The metakaolin was purchased from Tianjin Hongqiao District Tianbao Haotong Stone Processing Plant; Solid sodium silicate powder was purchased from Shandong Weilin Chemical Co., Ltd. Anhydrous potassium carbonate was purchased from Jinan Jiayang Chemical Co., Ltd. The insulating glass microspheres were purchased from Guangzhou Naiboshi Building Materials Co., Ltd. Redispersible latex powder was purchased from Changzhou Longheng Building Materials Technology Co., Ltd. The hydrophobic polycarboxylate superplasticizer was purchased from Jinan Quanchi New Materials Co., Ltd. Hydroxypropyl methylcellulose ether was purchased from Jinzhou Xincheng Cellulose Co., Ltd. Hydrophilic nano-silica A200 was purchased from Zhongbei Fine Chemical Co., Ltd.

[0053] The preparation method of the inorganic decorative solid aggregate material includes the following specific steps: S1: Silicate cement, metakaolin, granulated blast furnace slag powder, redispersible latex powder, and hydroxypropyl methylcellulose ether are mixed in a mixer for the first time at a speed of 400 rpm for 8 minutes to obtain a basic mixture. S2.1: Preparation of hydrophobically modified rutile titanium dioxide: Ordinary titanium dioxide was mixed with deionized water in a reactor to prepare a uniformly dispersed slurry. The pH of the slurry was adjusted to 10 with sodium hydroxide and stirred at 1000 rpm to disperse it thoroughly. Sodium silicate solution and aluminum sulfate solution were added to the slurry at 55°C. After coating, the slurry was filtered and washed with a large amount of deionized water. The washed filter cake was re-slurried in water. Octyltriethoxysilane was mixed with 150 mL of anhydrous ethanol and then 300 mL of deionized water was added. The mixture was then slowly added to the slurry and reacted at 70°C with continuous stirring for 2 hours. After the reaction was completed, the treated slurry was spray-dried or flash-dried to obtain dry hydrophobically modified rutile titanium dioxide. S2.2: The hydrophobically modified rutile titanium dioxide, hollow glass microspheres and the basic mixture described in step S1 are mixed for a second time. The second mixing speed is 150 rpm and the time is 10 min. S3.1: Preparation of the crystallizing activator: Metakaolin was mixed in a mixer at 300 rpm and heated to a uniform temperature of 45°C. Silane coupling agent KH 550 was diluted with twice its mass of anhydrous ethanol, with a mass ratio of metakaolin to silane coupling agent of 80:1. The solution was evenly sprayed onto the preheated metakaolin under stirring using an atomizing spray gun for 4 minutes. The rotation speed was then increased to 700 rpm. After spraying, the mixture was continued at 45°C for 10 minutes. The rotation speed was adjusted to 450 rpm, and hydrophilic nano-silica was sprayed into the mixture at a mass ratio of 80:8. The feeding time was controlled at 7 minutes. After feeding, the mixture was continued at 500 rpm for 15 minutes. The mixture was cooled to room temperature and passed through a 100-mesh sieve to obtain the core-shell structure crystallizing activator. S3.2: Solid sodium silicate powder, anhydrous potassium carbonate, hydrophobic polycarboxylate superplasticizer and core-shell structure crystallizing activator are mixed with the mixture treated in step S2 for a third mixing. The third mixing speed is 100 rpm and the time is 5 min to obtain the inorganic decorative whole aggregate material dry powder. S4: Inorganic decorative aggregate material and water are mixed at a mass ratio of 1:0.2, first mixed at 300 rpm for 60 seconds, and then dispersed at 1000 rpm for 120 seconds; and the slurry is allowed to stand and mature for 15 minutes before application.

[0054] Example 2 This embodiment is basically the same as Embodiment 1, except that it contains 25 parts silicate cement, 13 parts metakaolin, 6 parts S95 grade granulated blast furnace slag powder, 3 parts solid sodium silicate powder, 2 parts anhydrous potassium carbonate, 12 parts rutile titanium dioxide, 37.5 parts hollow glass microspheres, 3 parts crystallization activator, 2 parts redispersible latex powder, 1 part hydrophobic polycarboxylate superplasticizer, and 0.3 parts hydroxypropyl methylcellulose ether.

[0055] Example 3 This embodiment is basically the same as Embodiment 1, except that it contains 26 parts silicate cement, 13 parts metakaolin, 6.3 parts S95 grade granulated blast furnace slag powder, 3.2 parts solid sodium silicate powder, 1.8 parts anhydrous potassium carbonate, 10 parts rutile titanium dioxide, 39 parts hollow glass microspheres, 4 parts crystallization activator, 2.3 parts redispersible latex powder, 0.9 parts hydrophobic polycarboxylate superplasticizer, and 0.4 parts hydroxypropyl methylcellulose ether.

[0056] Example 4 This embodiment is basically the same as Embodiment 1, except that it contains 24 parts silicate cement, 12 parts metakaolin, 6.5 parts S95 grade granulated blast furnace slag powder, 3.2 parts solid sodium silicate powder, 1.8 parts anhydrous potassium carbonate, 10 parts rutile titanium dioxide, 42 parts hollow glass microspheres, 5 parts crystallizing activator, 2.3 parts redispersible latex powder, 0.9 parts hydrophobic polycarboxylate superplasticizer, and 0.3 parts hydroxypropyl methylcellulose ether.

[0057] Example 5 This embodiment is basically the same as Embodiment 1, except that it contains 24 parts silicate cement, 12 parts metakaolin, 7 parts S95 grade granulated blast furnace slag powder, 4 parts solid sodium silicate powder, 2.2 parts anhydrous potassium carbonate, 12 parts rutile titanium dioxide, 40 parts hollow glass microspheres, 4 parts crystallization activator, 3 parts redispersible latex powder, 0.9 parts hydrophobic polycarboxylate superplasticizer, and 0.3 parts hydroxypropyl methylcellulose ether.

[0058] Comparative Example 1 This comparative example is basically the same as Example 1, except that the preparation method of the core-shell structure crystallizing activator is replaced by simple physical blending of metakaolin and crystalline waterproofing agent.

[0059] Comparative Example 2 This comparative example is basically the same as Example 1, except that ordinary rutile titanium dioxide (without hydrophobic modification treatment) is used.

[0060] Comparative Example 3 This comparative example is basically the same as Example 1, except that all raw materials are added at once during preparation and mixed at 800 rpm for 15 minutes.

[0061] Comparative Example 4 This comparative example is basically the same as Example 1, except that the functional composite filler is replaced with ordinary quartz powder.

[0062] Experimental Case Performance tests were conducted on the inorganic decorative solid aggregate materials of Examples 1-5 and Comparative Examples 1-4. The thermal conductivity was tested according to ASTM C518, with an average temperature of 24℃ and a sample thickness of 10mm. The self-healing performance was tested using the pre-cracking method, where a 0.3mm wide crack was artificially created and observed under a microscope at regular intervals at a temperature of 23±2℃ and a relative humidity of 60±5%. The results are shown in Table 1.

[0063]

[0064] As shown in Table 1, the 7-day impermeability pressure of Examples 1-5 was all 1.0 MPa or higher, while that of Comparative Example 1 was 0.8 MPa, Comparative Example 3 was 0.9 MPa, and Comparative Example 4 was only 0.6 MPa. This indicates that the preparation method and raw material formulation used in this invention have significant advantages in improving the impermeability of the material, especially the use of the unique core-shell structure crystallizing activator, which can effectively fill the pores of the material and prevent water penetration.

[0065] Regarding the 28-day compressive strength, Examples 1-5 all reached over 40 MPa, with Example 3 reaching 48.2 MPa. In contrast, Comparative Example 3 only achieved a compressive strength of 38.5 MPa, indicating that the stepwise mixing process helps the raw materials react fully, forming a more stable structure and thus improving the compressive strength of the material.

[0066] Crack repair rate is an important indicator for evaluating the self-healing performance of materials. Examples 1-5 all achieved crack repair rates exceeding 90% after 28 days, while Comparative Example 1 only achieved 50%, and Comparative Example 4 only 10%. This may be because the core-shell structured crystallizing activator can form crystals at the crack site, filling it, and the continuous secondary hydration reaction of active mineral admixtures such as metakaolin in an alkaline environment also contributes to crack repair. However, Comparative Example 1 used a simple physically blended crystallizing activator, which failed to form an effective crystalline filling structure; Comparative Example 4 used ordinary quartz powder as a substitute for the functional composite filler, lacking active ingredients and thus failing to achieve a good self-healing effect.

[0067] Regarding thermal conductivity, the thermal conductivity of Examples 1-5 is at a low level, ranging from 0.059 to 0.068 W / m·K. This is due to the use of lightweight materials such as hollow glass microspheres, whose internal hollow structure effectively hinders heat transfer. However, Comparative Example 3, due to an unreasonable preparation process, resulted in an insufficiently dense material structure, causing its thermal conductivity to increase to 0.085 W / m·K. Comparative Example 4 used ordinary quartz powder, which has poor thermal conductivity, resulting in a significant increase in the material's thermal conductivity to 0.35 W / m·K.

[0068] Based on the comprehensive performance test results, the inorganic decorative solid aggregate material and its preparation method provided by this invention have significant advantages. Through a reasonable raw material formulation and unique preparation process, the material's impermeability, compressive strength, and self-healing properties can be significantly improved, while its thermal conductivity is reduced. This inorganic decorative solid aggregate material has broad application prospects in integrated exterior wall insulation and decoration systems and interior decorative wall surfaces, providing buildings with better insulation, waterproofing, and self-healing properties, thereby improving building quality and service life. It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. An inorganic decorative solid aggregate material, characterized in that, The product is expressed in parts by mass and includes the following components: 35-50 parts of composite cementitious material; 3-7 parts of composite alkali activator; 45-60 parts of functional composite filler; 2-6 parts of crystallization activator; 1.5-4.0 parts of polymer powder; 0.5-1.5 parts of water-repellent water-reducing agent; 0.1-0.5 parts of water-retaining agent; The functional composite filler includes pigments and heat-insulating fillers; The crystalline activator comprises a composite structure with metakaolin as the core and a crystalline waterproofing agent and a nano-nucleating agent as the shell.

2. The inorganic decorative solid aggregate material according to claim 1, characterized in that, The pigment in the functional composite filler is hydrophobically modified rutile titanium dioxide, and its dosage is 8-12 parts. The heat-insulating filler is hollow glass microspheres, and its dosage is 35-48 parts; and the true density of the hollow glass microspheres is 0.15-0.35 g / cm³. 3 The compressive strength is not less than 10 MPa.

3. The inorganic decorative solid aggregate material according to claim 1, characterized in that, In the crystallizing activator, the core has a specific surface area of ​​not less than 15000 m². 2 / kg metakaolin; the nano-nucleating agent in the shell is nano-silica; The mass ratio of the crystalline waterproofing agent to the metakaolin is 1:3~6.

4. The inorganic decorative solid aggregate material according to claim 1, characterized in that, The preparation method of the crystallizing activator is as follows: (1) Mechanical activation of metakaolin by mixing it at 200-300 rpm; (2) Add silane coupling agent to metakaolin and increase the rotation speed to 600~800 rpm to obtain a mixture; (3) Adjust the rotation speed to 400~500 rpm and spray nano-silica into the mixture; then add crystalline waterproofing agent and continue mixing to coat; (4) Cool and sieve.

5. The inorganic decorative solid aggregate material according to claim 1, characterized in that, The composite cementitious material includes silicate cement, metakaolin, and granulated blast furnace slag powder. The composite alkali activator comprises solid sodium silicate and carbonate.

6. A method for preparing an inorganic decorative solid aggregate material, characterized in that, The preparation of the inorganic decorative solid aggregate material according to any one of claims 1 to 5 includes the following steps: S1: The composite cementitious material, the polymer powder and the water-retaining agent are mixed in a first mixture to obtain a basic mixture; S2: The functional composite filler is mixed with the base mixture for a second time; S3: The composite alkali activator, the hydrophobic water-reducing agent, and the core-shell structure crystallizing activator are mixed with the mixture treated in step S2 in a third mixing process to obtain the inorganic decorative solid aggregate material.

7. The method for preparing inorganic decorative solid aggregate material according to claim 6, characterized in that, The first mixing speed is 400~500 rpm and the time is 5~10 min; the second mixing speed is 100~200 rpm and the time is 8~12 min; the third mixing speed is 80~120 rpm and the time is 3~8 min.

8. The application of an inorganic decorative solid aggregate material as described in any one of claims 1 to 5, characterized in that, The inorganic decorative aggregate material is used to prepare an integrated system for building exterior wall insulation and decoration, and / or interior decorative wall surfaces.

9. The application of the inorganic decorative solid aggregate material according to claim 8, characterized in that, The inorganic decorative aggregate material is mixed with water at a mass ratio of 1:(0.18~0.25) and stirred to form a slurry.

10. The application of the inorganic decorative solid aggregate material according to claim 8, characterized in that, The stirring process includes mixing at a speed of 200-400 rpm for 30-90 seconds, followed by high-speed dispersion at a speed of 800-1100 rpm for 90-180 seconds; and the slurry is allowed to stand and mature for 5-20 minutes before application.

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