A super-hydrophobic material based on retired wind power blade powder, a preparation method thereof and hydrophobic concrete containing the same

Abstract

This invention discloses a superhydrophobic material based on decommissioned wind turbine blade powder, its preparation method, and hydrophobic concrete containing the same. The superhydrophobic material is obtained by ultrasonically dispersing decommissioned wind turbine blade powder in anhydrous ethanol, followed by the sequential addition of water, a coupling agent, an alkanol mixture, a catalyst, a siloxane modifier, and nano-titanium dioxide for a composite reaction. The alkanol mixture is obtained by mixing n-hexane and isopropanol in a 1:1 volume ratio. The decommissioned wind turbine blade powder is obtained by pre-treating, crushing, grinding, removing resin from decommissioned wind turbine blades, and then grading the powder. Hydrophobic concrete is obtained by mixing the superhydrophobic material with cement, natural coarse aggregate, natural sand, a water-reducing agent, and water. This invention, by modifying decommissioned wind turbine blade powder to obtain a superhydrophobic material, and then adding it to the concrete mixture, can effectively improve the impermeability of concrete and greatly enhance the durability of the concrete structure.

Description

Technical Field

[0001] This invention belongs to the field of solid waste resource utilization and functional materials technology, specifically relating to a superhydrophobic material based on decommissioned wind turbine blade powder, its preparation method, and hydrophobic concrete containing it. Background Technology

[0002] With the booming development of the wind power industry, the first batch of large-scale wind turbine generators are gradually entering their decommissioning period. As a core composite material component, the disposal of wind turbine blades has become a global environmental and resource challenge. Blades are mainly composed of thermosetting composite materials such as glass fiber and resin, which are chemically stable and difficult to degrade naturally. Traditional landfill disposal methods not only occupy a large amount of land resources but also pose potential environmental pollution risks. Therefore, developing high-value, resource-based recycling technologies for decommissioned wind turbine blades is of great significance for promoting the sustainable development of the wind power industry.

[0003] In the field of building materials, the durability of concrete directly determines the service life and safety of building structures. Concrete is a hydrophilic porous material, susceptible to damage from water and corrosive ions in the environment (such as Cl-). SO4 2 Water can easily penetrate the concrete through capillary channels, directly causing steel corrosion, freeze-thaw damage, and sulfate attack. Simultaneously, contaminants easily adhere to the concrete surface, microorganisms proliferate, and moisture retention in cold environments significantly increases the risk of freezing. These derivative problems caused by water and porosity collectively exacerbate concrete deterioration and threaten its safe use. Therefore, improving the durability of concrete is urgently needed.

[0004] Superhydrophobic materials have shown great potential in improving the durability of concrete due to their extreme water-repellent properties. By constructing a superhydrophobic layer on or inside the concrete surface, the intrusion of liquid water can be effectively blocked, thereby delaying the occurrence of various durability defects at the source. However, current methods for preparing superhydrophobic concrete mostly rely on complex chemical vapor deposition and etching processes, resulting in high costs and cumbersome processes, making it difficult to apply on a large scale in civil engineering. Summary of the Invention

[0005] To address the problems existing in the background technology mentioned above, the present invention provides a superhydrophobic material based on decommissioned wind turbine blade powder, its preparation method, and hydrophobic concrete containing it. The superhydrophobic material is obtained by modifying the decommissioned wind turbine blade powder, and then added to the concrete mixture, which can effectively improve the impermeability of the concrete and greatly improve the durability of the concrete structure.

[0006] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0007] A superhydrophobic material based on decommissioned wind turbine blade powder comprises the following raw material components in parts by weight:

[0008] 60-150 parts of decommissioned wind turbine blade powder

[0009] 2-15 parts of coupling agent,

[0010] 1-50 parts of siloxane modifier

[0011] 3-20 parts of nano titanium dioxide

[0012] 50-150 parts of an alkanol mixture,

[0013] Catalyst 0.5~5 parts,

[0014] 100-800 parts of anhydrous ethanol

[0015] 2-15 parts water;

[0016] The alkanol mixture was obtained by mixing n-hexane and isopropanol in a volume ratio of 1:1.

[0017] The decommissioned wind turbine blade powder is obtained by pre-treatment, crushing, grinding, resin removal, and grading of decommissioned wind turbine blades. The main components of the decommissioned wind turbine blades are glass fiber and resin. The decommissioned wind turbine blades are first pre-treated to remove secondary components such as sandwich structure materials, and then crushed and ground. Finally, the resin is removed by existing methods such as heat treatment, flocculation, or electrostatic separation. Heat treatment is preferred for resin removal. After the heat-treated powder is cooled to room temperature, it is ground to a particle size of 200-10000 mesh, preferably 300-1200 mesh. Existing grinding methods such as high-speed mechanical crushing, ball milling, or air jet milling can be used for grinding. Ball milling is preferred. The speed of the ball mill is 800-1200 r / min, and the grinding time is 1-4 hours.

[0018] Furthermore, the heat treatment method is as follows: the decommissioned wind turbine blade product after pretreatment, crushing and grinding is placed in a furnace containing inert gas at a temperature of 400~700℃ for heat treatment for 0.5~2 hours to remove resin; the heat treatment temperature and time are preferably determined based on the thermogravimetric analysis results to ensure complete decomposition of resin.

[0019] The superhydrophobic material is obtained by ultrasonically dispersing decommissioned wind turbine blade powder in anhydrous ethanol, followed by the sequential addition of water, coupling agent, alkanol mixture, catalyst, siloxane modifier, and nano-titanium dioxide for composite reaction.

[0020] Preferably, the raw material components of the superhydrophobic material based on decommissioned wind turbine blade powder are as follows by weight:

[0021] 70-130 parts of decommissioned wind turbine blade powder,

[0022] 4-10 parts of coupling agent,

[0023] 5-25 parts of siloxane modifier,

[0024] 5-15 parts of nano titanium dioxide

[0025] 80-100 parts of an alkanol mixture,

[0026] 1-3 parts catalyst

[0027] 300-500 parts of anhydrous ethanol

[0028] 4-10 parts water.

[0029] Furthermore, the coupling agent of the present invention is selected from any one or a mixture of one or more of silanes, titanates, zirconates and aluminum-titanium composite coupling agents, preferably silane coupling agents, specifically selected from any one or a mixture of one or more of vinyltriethoxysilane, propenyltrimethoxysilane and 3-aminopropyltriethoxysilane.

[0030] Furthermore, the siloxane modifier of the present invention is selected from any one or a mixture of more than one of polymethylhydrosiloxane, polydimethylsiloxane, polydiethylsiloxane, methyltrimethoxysilane, and hexadecyltrimethoxysilane, preferably polymethylhydrosiloxane or polydimethylsiloxane.

[0031] Furthermore, the catalyst described in this invention is a noble metal catalyst, preferably a platinum catalyst.

[0032] Furthermore, the nano-titanium dioxide described in this invention is commercially available nano-titanium dioxide with a particle size of 20~40nm.

[0033] Furthermore, the present invention also provides a method for preparing a superhydrophobic material based on decommissioned wind turbine blade powder, comprising: firstly, ultrasonically dispersing the decommissioned wind turbine blade powder in anhydrous ethanol; secondly, adding water and a coupling agent for surface pretreatment; then adding an alkanol mixture, followed by the sequential addition of a catalyst and a siloxane modifier; finally, adding a nano-titanium dioxide suspension for grafting and composite reaction, and after washing, drying, and grinding to a certain fineness, a superhydrophobic material with both superhydrophobic and photocatalytic functions can be obtained.

[0034] The superhydrophobic material has a fineness of 300~1200 mesh.

[0035] The preparation method specifically includes the following steps:

[0036] (1) The retired wind turbine blade powder was added to anhydrous ethanol and ultrasonically treated to fully disperse it, with a ratio of 1:3 between the mass / g of the retired wind turbine blade powder and the volume / mL of anhydrous ethanol, to obtain solution A; nano titanium dioxide was added to the remaining anhydrous ethanol and ultrasonically treated, with the preferred ratio of nano titanium dioxide mass / g to anhydrous ethanol volume / mL being 1:10, to obtain a uniform nano titanium dioxide suspension, denoted as solution B;

[0037] The ultrasonic frequencies are all 20~60kHz, and the ultrasonic processing times are all 5~20min.

[0038] (2) Under stirring, water and silane coupling agent are added dropwise to solution A obtained in step (1) at a constant rate of 1-3 drops / second. After the addition is completed, the mixture is stirred at room temperature for 5-20 minutes to allow the silane coupling agent to be fully hydrolyzed and to undergo a coupling reaction with the active groups on the powder surface. Then, an alkanol mixture is added to it. Under stirring, catalyst and siloxane modifier are added dropwise at a constant rate of 1-3 drops / second. After the addition is completed, the mixture is stirred at 40-80℃ for 5-20 minutes to allow the long-chain siloxane to be grafted onto the surface of the decommissioned wind turbine blade powder, fundamentally giving it hydrophobic properties, and obtaining mixture C.

[0039] (3) Slowly and evenly add the solution B obtained in step (1) to the mixture C in step (2), and stir and react at 40~80℃ for 10~30min to fully combine the nano titanium dioxide particles with the surface-modified decommissioned wind turbine blade powder to jointly construct a micro-nano rough structure and obtain a slurry.

[0040] (4) Dry the slurry obtained in step (3) to constant weight, and then grind it to 300~1200 mesh to obtain a superhydrophobic material with active glass fiber as the skeleton, uniformly composited nano titanium dioxide on the surface and modified by a long chain siloxane layer.

[0041] The superhydrophobic material based on decommissioned wind turbine blade powder described in this invention can improve the hydrophobic properties of concrete, thereby enhancing its impermeability. Combining the Laplace equation (1), its hydrophobic principle is as follows:

[0042]

[0043] Where, Δ P This indicates capillary pressure in Pa. σ This represents the surface tension of the pore solution in N / m. θ This indicates the contact angle (°) between the liquid and the inner wall of the capillary. r This indicates the radius of the capillary in meters (m).

[0044] For ordinary concrete, capillary absorption is a spontaneous thermodynamic process when the contact angle is below 90°. This process is characterized by molecular attraction between the liquid and the matrix, leading to capillary rise and liquid surface depression. However, with the incorporation of superhydrophobic decommissioned wind turbine blade powder, the low surface energy groups (methyl groups) it carries increase the contact angle of the concrete to above 90°. The reversal of the pressure difference means that water requires more energy to penetrate into the pores, thereby reducing the water absorption rate of the concrete.

[0045] Furthermore, the present invention also provides a hydrophobic concrete comprising the above-mentioned superhydrophobic material, comprising the following raw material components in parts by weight:

[0046] 200-400 parts cement

[0047] 860-1140 parts of natural coarse aggregate,

[0048] 600-740 parts natural sand

[0049] 5-40 parts of superhydrophobic material

[0050] Water-reducing agent 0.5~2 parts,

[0051] 120-200 parts water.

[0052] Preferably, the raw material components of the hydrophobic concrete are as follows by weight:

[0053] 250-350 parts cement

[0054] 960-1080 parts of natural coarse aggregate,

[0055] 630-690 parts natural sand

[0056] 6-24 parts of superhydrophobic material

[0057] Water-reducing agent 0.7~1.3 parts,

[0058] 130-170 parts water.

[0059] Furthermore, the cement is PO 42.5 ordinary Portland cement with an average particle size of 10~34μm and a 28-day compressive strength of 44.6~51.2MPa.

[0060] Furthermore, the natural coarse aggregate is 5-20mm natural crushed stone aggregate with an apparent density of 2600-2800 kg / m³. 3 The bulk density is 1410~1630 kg / m³ 3 .

[0061] Furthermore, the fineness modulus of the natural sand is 2.4 to 3.0, and the average particle size is 0.30 to 0.60 mm.

[0062] Furthermore, the water-reducing agent is a polycarboxylate high-performance water-reducing agent with a water reduction rate of 22% to 28%.

[0063] Furthermore, the present invention also provides a method for preparing the above-mentioned hydrophobic concrete, comprising the following steps:

[0064] (1) Take samples of natural coarse aggregate and natural sand according to the component content in the mix proportion, and pour them into the concrete mixer in sequence and dry mix for 0.5~2 minutes;

[0065] (2) Take samples of cement and superhydrophobic material according to the component content in the mix proportion, mechanically stir for 0.5 to 2 minutes until macroscopically uniform to form a premix, and then add it to the concrete mixer and dry mix for 0.5 to 3 minutes;

[0066] (3) Take samples of water and water-reducing agent according to the component content in the ratio, pre-stir in a container for 0.5 to 2 minutes to form a uniform and stable diluted solution, and then slowly add it to the concrete mixer and stir for 1 to 3 minutes to obtain a hydrophobic fresh concrete mixture.

[0067] (4) The hydrophobic fresh concrete mixture obtained in step (3) is poured into concrete specimens, then compacted on a vibrating table, and demolded after standing at room temperature for 24 hours. After curing for 28 days under standard curing conditions of 20℃±2℃ and relative humidity above 95%, the hydrophobic concrete of the present invention is obtained and its performance is tested.

[0068] In step (4), the specimen size can be designed as a cube specimen of 100mm×100mm×100mm and a prism specimen of 100mm×100mm×400mm.

[0069] Compared with the prior art, the present invention has the following advantages:

[0070] (1) The decommissioned wind turbine blade powder obtained by heat treatment and grinding in this invention is mainly composed of micro- and nano-sized glass fibers, which physically overlap and interlock in multiple dimensions to form a dense network structure, effectively blocking the channels for moisture migration. More importantly, the decommissioned wind turbine blade powder obtained after treatment has a good micro-aggregate filling effect, and its surface activity is enhanced, which can reduce the size and number of micropores in concrete and improve the density of the matrix. The superhydrophobic modification of this invention, while retaining its original fiber structure and chemical activity, additionally endows it with extremely strong water repellency.

[0071] (2) This invention uses retired wind turbine blade powder as a micro-nano structure skeleton. Through surface chemical modification and functional composite, it not only endows it with durable superhydrophobic properties, but also introduces the photocatalytic activity of nano titanium dioxide. When it is incorporated into concrete, it can significantly improve impermeability and durability, and bring synergistic effects such as self-cleaning, pollutant degradation and anti-icing. It not only realizes the high added value recycling of waste composite materials, but also provides a green and economical new material solution for improving the service performance of civil engineering structures.

[0072] (3) The deterioration of concrete often begins with the intrusion of external moisture and corrosive ions. This invention utilizes powder from retired wind turbine blades to prepare superhydrophobic materials. When these materials are incorporated into concrete, they can form uniformly distributed superhydrophobic points inside and on the surface of the concrete. When moisture comes into contact with these modified powders, the extremely high contact angle makes it difficult for droplets to spread and be adsorbed, thereby significantly inhibiting capillary adsorption and preventing moisture from entering the concrete. This effectively delays sulfate corrosion, steel corrosion, and freeze-thaw damage caused by water, and greatly extends the service life of concrete structures.

[0073] (4) By grafting a siloxane modifier onto the surface of decommissioned wind turbine blade powder, organic long-chain alkyl groups were successfully introduced into the inorganic powder, giving it superhydrophobicity. In existing technologies, this is typically used to increase the dispersibility of certain particles in organic systems and reduce agglomeration. This invention creatively applies this technology to concrete, an inorganic material system, achieving a complementary advantage between organic and inorganic materials, and providing a novel and efficient technical approach to solving the durability problem of concrete.

[0074] (5) The introduction of nano-titanium dioxide further enhances the multifunctional properties of the material. Its photocatalytic properties enable the concrete surface to decompose organic pollutants (such as oil stains, algae, etc.) under light, achieving a self-cleaning effect and reducing maintenance costs; at the same time, it can degrade harmful gases in the air (such as NO). x SO x (etc.) to improve surrounding air quality. Furthermore, the synergistic effect of superhydrophobic surfaces and photocatalysis effectively reduces moisture retention and ice nucleation, thereby lowering the risk of icing and improving the anti-icing performance of concrete in winter or cold regions. This provides a comprehensive improvement in the environmental adaptability and durability of concrete structures.

[0075] (6) This invention provides a new solution for the recycling of wind turbine blades. Through heat treatment and surface modification, retired wind turbine blades, a difficult-to-dispose-of solid waste, are transformed into superhydrophobic functional materials that can be used in high-performance concrete. This technology aims to open up a new path for the high-value utilization of solid waste, and thereby achieve resource regeneration while eliminating environmental pollution by replacing traditional cementitious materials, thus building a green closed loop for the wind power industry. Detailed Implementation

[0076] The present invention will now be described in detail with reference to specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0077] A superhydrophobic material based on decommissioned wind turbine blade powder comprises the following raw material components in parts by weight:

[0078] 60-150 parts of decommissioned wind turbine blade powder

[0079] 2-15 parts of coupling agent,

[0080] 1-50 parts of siloxane modifier

[0081] 3-20 parts of nano titanium dioxide

[0082] 50-150 parts of an alkanol mixture,

[0083] Catalyst 0.5~5 parts,

[0084] 100-800 parts of anhydrous ethanol

[0085] 2-15 parts water;

[0086] The alkanol mixture was obtained by mixing n-hexane and isopropanol in a volume ratio of 1:1.

[0087] The decommissioned wind turbine blade powder is obtained by pre-treatment, crushing, grinding, resin removal, and grading of decommissioned wind turbine blades. The main components of the decommissioned wind turbine blades are glass fiber and resin. The decommissioned wind turbine blades are first pre-treated to remove secondary components such as sandwich structure materials, and then crushed and ground. Finally, the resin is removed by existing methods such as heat treatment, flocculation, or electrostatic separation. Heat treatment is preferred for resin removal. After the heat-treated powder is cooled to room temperature, it is ground to a particle size of 200-10000 mesh, preferably 300-1200 mesh. Existing grinding methods such as high-speed mechanical crushing, ball milling, or air jet milling can be used for grinding. Ball milling is preferred. The speed of the ball mill is 800-1200 r / min, and the grinding time is 1-4 hours.

[0088] Furthermore, the heat treatment method is as follows: the decommissioned wind turbine blade product after pretreatment, crushing and grinding is placed in a furnace containing inert gas at a temperature of 400~700℃ for heat treatment for 0.5~2 hours to remove resin; the heat treatment temperature and time are preferably determined based on the thermogravimetric analysis results to ensure complete decomposition of resin.

[0089] The superhydrophobic material is obtained by ultrasonically dispersing decommissioned wind turbine blade powder in anhydrous ethanol, followed by the sequential addition of water, coupling agent, alkanol mixture, catalyst, siloxane modifier, and nano-titanium dioxide for composite reaction.

[0090] Preferably, the raw material components of the superhydrophobic material based on decommissioned wind turbine blade powder are as follows by weight:

[0091] 70-130 parts of decommissioned wind turbine blade powder,

[0092] 4-10 parts of coupling agent,

[0093] 5-25 parts of siloxane modifier,

[0094] 5-15 parts of nano titanium dioxide

[0095] 80-100 parts of an alkanol mixture,

[0096] 1-3 parts catalyst

[0097] 300-500 parts of anhydrous ethanol

[0098] 4-10 parts water.

[0099] Furthermore, the coupling agent of the present invention is selected from any one or a mixture of one or more of silanes, titanates, zirconates and aluminum-titanium composite coupling agents, preferably silane coupling agents, specifically selected from any one or a mixture of one or more of vinyltriethoxysilane, propenyltrimethoxysilane and 3-aminopropyltriethoxysilane.

[0100] Furthermore, the siloxane modifier of the present invention is selected from any one or a mixture of more than one of polymethylhydrosiloxane, polydimethylsiloxane, polydiethylsiloxane, methyltrimethoxysilane, and hexadecyltrimethoxysilane, preferably polymethylhydrosiloxane or polydimethylsiloxane.

[0101] Furthermore, the catalyst described in this invention is a noble metal catalyst, preferably a platinum catalyst.

[0102] Furthermore, the nano-titanium dioxide described in this invention is commercially available nano-titanium dioxide with a particle size of 20~40nm.

[0103] Furthermore, the present invention also provides a method for preparing a superhydrophobic material based on decommissioned wind turbine blade powder, comprising: firstly, ultrasonically dispersing the decommissioned wind turbine blade powder in anhydrous ethanol; secondly, adding water and a coupling agent for surface pretreatment; then adding an alkanol mixture, followed by the sequential addition of a catalyst and a siloxane modifier; finally, adding a nano-titanium dioxide suspension for grafting and composite reaction, and after washing, drying, and grinding to a certain fineness, a superhydrophobic material with both superhydrophobic and photocatalytic functions can be obtained.

[0104] The superhydrophobic material has a fineness of 300~1200 mesh.

[0105] Example 1

[0106] A superhydrophobic material based on decommissioned wind turbine blade powder is compounded from the following raw materials in parts by weight: 100 parts decommissioned wind turbine blade powder, 7 parts vinyltriethoxysilane, 15 parts polymethylhydrosiloxane, 90 parts n-hexane + isopropanol (volume ratio 1:1), 2 parts platinum catalyst, 10 parts nano titanium dioxide, 400 parts anhydrous ethanol, and 7 parts water.

[0107] Specifically, the preparation steps of a superhydrophobic material based on decommissioned wind turbine blade powder are as follows: ① After pretreatment, crushing, and grinding, the decommissioned wind turbine blades are placed in a furnace containing inert gas N2 at a temperature of 550℃ for 1 hour to remove resin. After cooling to room temperature, they are then ground in a planetary ball mill at a speed of 1000 r / min for 3 hours to refine the powder to 1200 mesh, obtaining decommissioned wind turbine blade powder; ② The decommissioned wind turbine blade powder obtained after treatment is added to anhydrous ethanol at a ratio of powder mass (g) to anhydrous ethanol volume (mL) of 1:3, and treated under ultrasonic conditions at a frequency of 40 kHz for 10 minutes to ensure thorough dispersion, obtaining solution A; Nano-titanium dioxide is added to anhydrous ethanol at a ratio of its mass (g) to anhydrous ethanol volume (mL) of 1:10, and treated under ultrasonic conditions at a frequency of 40 kHz for 10 minutes, obtaining a uniform nano-titanium dioxide suspension, denoted as solution B; ③ The solution is stirred... In step A, water and silane coupling agent are added sequentially at a constant rate of 2 drops / second. After the addition is complete, the mixture is stirred for 10 minutes to allow the silane coupling agent to be fully hydrolyzed and to undergo a coupling reaction with the active groups on the powder surface. Then, a mixed solution of n-hexane and isopropanol is added. While stirring, a catalyst and a siloxane modifier are added sequentially at a constant rate of 2 drops / second. After the addition is complete, the mixture is stirred at 60°C for 10 minutes to allow the long-chain siloxane to be grafted onto the surface of the decommissioned wind turbine blade powder through a hydrogenation reaction, fundamentally endowing it with hydrophobic properties, resulting in mixture C. Solution B is slowly added to mixture C and stirred at 60°C for 20 minutes to allow the nano-titanium dioxide particles to fully combine with the surface-modified decommissioned wind turbine blade powder, jointly constructing a micro-nano rough structure, resulting in a slurry. The slurry is dried to constant weight and then ground to 1200 mesh to obtain a superhydrophobic material with active glass fiber as the skeleton, uniformly composited nano-titanium dioxide on the surface, and a chemically bonded low surface energy layer.

[0108] A method for preparing concrete containing superhydrophobic materials, comprising the following components by weight: 300 parts cement, 1020 parts natural coarse aggregate, 660 parts natural sand, 15 parts superhydrophobic material, 1 part water-reducing agent, and 150 parts water.

[0109] The cement used is PO 42.5 ordinary Portland cement with an average particle size of 15.66 μm and a 28-day compressive strength of 48.6 MPa; the natural coarse aggregate is 5-20 mm natural crushed stone aggregate with an apparent density of 2658 kg / m³. 3 The bulk density is 1457 kg / m³. 3 The fineness modulus of the natural sand is 2.9, and the average particle size is 0.37 mm. The water-reducing agent is a high-performance polycarboxylate water-reducing agent with a water reduction rate of 26%. The water is tap water supplied to the laboratory.

[0110] Specifically, the preparation steps of a concrete containing superhydrophobic materials are as follows: ① Sample natural coarse aggregate and natural sand according to the component content in the mix proportion, and pour them into a concrete mixer and dry mix for 1 minute; ② Sample cement and superhydrophobic materials according to the component content in the mix proportion, mechanically mix for 1 minute until macroscopically uniform to form a premix, and then add it to the concrete mixer and dry mix for 1 minute; ③ Sample water and water-reducing agent according to the component content in the mix proportion, pre-stir in a container for 1 minute to form a homogeneous and stable diluent, and then slowly add it to the concrete mixer and stir for 2 minutes to obtain a hydrophobic fresh concrete mixture; ④ Pour the fresh concrete mixture into 100mm×100mm×100mm cube specimens and 100mm×100mm×400mm prism specimens, then compact them on a vibrating table, let them stand at room temperature for 24 hours, remove the mold, and then cure them for 28 days under standard curing conditions of 20℃±2℃ and relative humidity above 95% before performance testing.

[0111] Example 2

[0112] A superhydrophobic material based on decommissioned wind turbine blade powder is composed of the following raw materials in parts by weight: 100 parts decommissioned wind turbine blade powder, 7 parts propylenetrimethoxysilane, 15 parts polymethylhydrosiloxane, 90 parts n-hexane + isopropanol (volume ratio 1:1), 2 parts platinum catalyst, 10 parts nano titanium dioxide, 400 parts anhydrous ethanol, and 7 parts water.

[0113] Specifically, the preparation steps of a superhydrophobic material based on decommissioned wind turbine blade powder are as follows: ① After pretreatment, crushing, and grinding, the decommissioned wind turbine blades are placed in a furnace containing inert gas N2 at a temperature of 400℃ for 2 hours to remove resin. After cooling to room temperature, they are then ground in a planetary ball mill at a speed of 1000 r / min for 3 hours to refine the powder to 1200 mesh, obtaining decommissioned wind turbine blade powder; ② The decommissioned wind turbine blade powder obtained after treatment is added to anhydrous ethanol at a ratio of powder mass (g) to anhydrous ethanol volume (mL) of 1:3, and treated under ultrasonic conditions at a frequency of 20 kHz for 20 minutes to ensure thorough dispersion, obtaining solution A; Nano-titanium dioxide is added to anhydrous ethanol at a ratio of its mass (g) to anhydrous ethanol volume (mL) of 1:10, and treated under ultrasonic conditions at a frequency of 20 kHz for 20 minutes, obtaining a uniform nano-titanium dioxide suspension, denoted as solution B; ③ The solution is stirred... In step A, water and silane coupling agent are added sequentially at a constant rate of 1 drop / second. After the addition is complete, the mixture is stirred for 20 minutes to allow the silane coupling agent to be fully hydrolyzed and coupled with the active groups on the powder surface. Then, a mixed solution of n-hexane and isopropanol is added. While stirring, a catalyst and siloxane modifier are added sequentially at a constant rate of 1 drop / second. After the addition is complete, the mixture is stirred at 40°C for 20 minutes to allow the long-chain siloxane to be grafted onto the surface of the decommissioned wind turbine blade powder through a hydrogenation reaction, fundamentally endowing it with hydrophobic properties, resulting in mixture C. Solution B is slowly added to mixture C and stirred at 40°C for 30 minutes to allow the nano-titanium dioxide particles to fully combine with the surface-modified decommissioned wind turbine blade powder, jointly constructing a micro-nano rough structure, resulting in a slurry. The slurry is dried to constant weight and then ground to 1200 mesh to obtain a superhydrophobic material with active glass fiber as the skeleton, uniformly composited nano-titanium dioxide on the surface, and a chemically bonded low surface energy layer.

[0114] A concrete containing a superhydrophobic material comprises, by weight, the following components: 300 parts cement, 1020 parts natural coarse aggregate, 660 parts natural sand, 15 parts superhydrophobic material, 1 part water-reducing agent, and 150 parts water.

[0115] The cement used is PO 42.5 ordinary Portland cement with an average particle size of 15.66 μm and a 28-day compressive strength of 48.6 MPa; the natural coarse aggregate is 5-20 mm natural crushed stone aggregate with an apparent density of 2658 kg / m³. 3 The bulk density is 1457 kg / m³. 3 The fineness modulus of the natural sand is 2.9, and the average particle size is 0.37 mm. The water-reducing agent is a high-performance polycarboxylate water-reducing agent with a water reduction rate of 26%. The water is tap water supplied to the laboratory.

[0116] Specifically, the preparation steps of concrete containing superhydrophobic materials are as follows: ① Sample natural coarse aggregate and natural sand according to the component content in the mix proportion, and pour them into a concrete mixer and dry mix for 0.5 minutes; ② Sample cement and superhydrophobic materials according to the component content in the mix proportion, mechanically mix for 0.5 minutes until macroscopically homogeneous to form a premix, and then add it to the concrete mixer and dry mix for 0.5 minutes; ③ Sample water and water-reducing agent according to the component content in the mix proportion, pre-mix in a container for 0.5 minutes, so that... A homogeneous and stable diluted solution is formed, which is then slowly added to a concrete mixer and stirred for 1 minute to obtain a hydrophobic fresh concrete mixture; ④ The fresh concrete mixture is poured into 100mm×100mm×100mm cube specimens and 100mm×100mm×400mm prism specimens, which are then compacted on a vibrating table, and demolded after standing at room temperature for 24 hours. After curing for 28 days under standard curing conditions of 20℃±2℃ and relative humidity above 95%, performance tests are conducted.

[0117] Example 3

[0118] A superhydrophobic material based on decommissioned wind turbine blade powder is compounded from the following raw materials in parts by weight: 100 parts decommissioned wind turbine blade powder, 7 parts aluminum-titanium composite coupling agent (HW-133), 15 parts polydimethylsiloxane, 90 parts n-hexane + isopropanol (volume ratio 1:1), 2 parts platinum catalyst, 10 parts nano titanium dioxide, 400 parts anhydrous ethanol, and 7 parts water.

[0119] Specifically, the preparation steps of a superhydrophobic material based on decommissioned wind turbine blade powder are as follows: ① After pretreatment, crushing, and grinding, the decommissioned wind turbine blades are placed in a furnace containing inert gas N2 at a temperature of 700℃ for 0.5 hours to remove resin. After cooling to room temperature, they are then ground in a planetary ball mill at a speed of 1000 r / min for 3 hours to refine the powder to 1200 mesh, obtaining decommissioned wind turbine blade powder; ② The decommissioned wind turbine blade powder obtained after treatment is added to anhydrous ethanol at a ratio of powder mass (g) to anhydrous ethanol volume (mL) of 1:3, and treated under ultrasonic conditions at a frequency of 60 kHz for 5 minutes to ensure thorough dispersion, obtaining solution A; Nano-titanium dioxide is added to anhydrous ethanol at a ratio of its mass (g) to anhydrous ethanol volume (mL) of 1:10, and treated under ultrasonic conditions at a frequency of 60 kHz for 5 minutes, obtaining a uniform nano-titanium dioxide suspension, denoted as solution B; ③ The solution is stirred... In liquid A, water and silane coupling agent are added sequentially at a constant rate of 3 drops / second. After the addition is complete, the mixture is stirred for 5 minutes to allow the silane coupling agent to be fully hydrolyzed and to undergo a coupling reaction with the active groups on the powder surface. Then, a mixed solution of n-hexane and isopropanol is added. While stirring, a catalyst and siloxane modifier are added sequentially at a constant rate of 3 drops / second. After the addition is complete, the mixture is stirred at 80°C for 5 minutes to allow the long-chain siloxane to be grafted onto the surface of the decommissioned wind turbine blade powder through a hydrogenation reaction, fundamentally endowing it with hydrophobic properties, resulting in mixed liquid C. ④ Solution B is slowly added to mixed liquid C and stirred at 80°C for 10 minutes to allow the nano-titanium dioxide particles to fully combine with the surface-modified decommissioned wind turbine blade powder, jointly constructing a micro-nano rough structure, resulting in a slurry. ⑤ The slurry is dried to constant weight and then ground to 1200 mesh to obtain a superhydrophobic material with active glass fiber as the skeleton, uniformly composited nano-titanium dioxide on the surface, and a chemically bonded low surface energy layer.

[0120] A concrete containing a superhydrophobic material comprises, by weight, the following components: 300 parts cement, 1020 parts natural coarse aggregate, 660 parts natural sand, 15 parts superhydrophobic material, 1 part water-reducing agent, and 150 parts water.

[0121] The cement used is PO 42.5 ordinary Portland cement with an average particle size of 15.66 μm and a 28-day compressive strength of 48.6 MPa; the natural coarse aggregate is 5-20 mm natural crushed stone aggregate with an apparent density of 2658 kg / m³. 3 The bulk density is 1457 kg / m³. 3 The fineness modulus of the natural sand is 2.9, and the average particle size is 0.37 mm. The water-reducing agent is a high-performance polycarboxylate water-reducing agent with a water reduction rate of 26%. The water is tap water supplied to the laboratory.

[0122] Specifically, the preparation steps of a concrete containing superhydrophobic materials are as follows: ① Sample natural coarse aggregate and natural sand according to the component content in the mix proportion, and pour them into a concrete mixer and dry mix for 2 minutes; ② Sample cement and superhydrophobic materials according to the component content in the mix proportion, mechanically mix for 2 minutes until macroscopically uniform to form a premix, and then add it to the concrete mixer and dry mix for 3 minutes; ③ Sample water and water-reducing agent according to the component content in the mix proportion, pre-stir in a container for 2 minutes to form a homogeneous and stable diluent, and then slowly add it to the concrete mixer and stir for 3 minutes to obtain a hydrophobic fresh concrete mixture; ④ Pour the fresh concrete mixture into 100mm×100mm×100mm cube specimens and 100mm×100mm×400mm prism specimens, then compact them on a vibrating table, let them stand at room temperature for 24 hours, remove the mold, and then cure them for 28 days under standard curing conditions of 20℃±2℃ and relative humidity above 95% before performance testing.

[0123] Example 4

[0124] A superhydrophobic material based on decommissioned wind turbine blade powder is formulated from the following raw materials in parts by weight: 70 parts decommissioned wind turbine blade powder, 7 parts titanate coupling agent (isopropyl tristearate titanate), 15 parts hexadecyltrimethoxysilane, 90 parts n-hexane + isopropanol (volume ratio 1:1), 2 parts platinum catalyst, 10 parts nano titanium dioxide, 400 parts anhydrous ethanol, and 7 parts water.

[0125] Specifically, the preparation of a superhydrophobic material based on decommissioned wind turbine blade powder is carried out according to the steps of Example 1.

[0126] A concrete containing a superhydrophobic material comprises, by weight, the following components: 300 parts cement, 1020 parts natural coarse aggregate, 660 parts natural sand, 15 parts superhydrophobic material, 1 part water-reducing agent, and 150 parts water.

[0127] The cement used is PO 42.5 ordinary Portland cement with an average particle size of 15.66 μm and a 28-day compressive strength of 48.6 MPa; the natural coarse aggregate is 5-20 mm natural crushed stone aggregate with an apparent density of 2658 kg / m³. 3 The bulk density is 1457 kg / m³. 3 The fineness modulus of the natural sand is 2.9, and the average particle size is 0.37 mm. The water-reducing agent is a high-performance polycarboxylate water-reducing agent with a water reduction rate of 26%. The water is tap water supplied to the laboratory.

[0128] Specifically, the preparation of a concrete containing superhydrophobic materials is carried out in accordance with the steps of Example 1.

[0129] Example 5

[0130] A superhydrophobic material based on decommissioned wind turbine blade powder is composed of the following raw materials in parts by weight: 130 parts decommissioned wind turbine blade powder, 7 parts zirconate coupling agent (Zr-801), 15 parts polymethylhydrosiloxane, 90 parts n-hexane + isopropanol (volume ratio 1:1), 2 parts platinum catalyst, 10 parts nano titanium dioxide, 400 parts anhydrous ethanol, and 7 parts water.

[0131] Specifically, the preparation of a superhydrophobic material based on decommissioned wind turbine blade powder is carried out according to the steps of Example 1.

[0132] A concrete containing a superhydrophobic material comprises, by weight, the following components: 300 parts cement, 1020 parts natural coarse aggregate, 660 parts natural sand, 15 parts superhydrophobic material, 1 part water-reducing agent, and 150 parts water.

[0133] The cement used is PO 42.5 ordinary Portland cement with an average particle size of 15.66 μm and a 28-day compressive strength of 48.6 MPa; the natural coarse aggregate is 5-20 mm natural crushed stone aggregate with an apparent density of 2658 kg / m³. 3 The bulk density is 1457 kg / m³. 3 The fineness modulus of the natural sand is 2.9, and the average particle size is 0.37 mm. The water-reducing agent is a high-performance polycarboxylate water-reducing agent with a water reduction rate of 26%. The water is tap water supplied to the laboratory.

[0134] Specifically, the preparation of a concrete containing superhydrophobic materials is carried out in accordance with the steps of Example 1.

[0135] Example 6

[0136] A superhydrophobic material based on decommissioned wind turbine blade powder is compounded from the following raw materials in parts by weight: 100 parts decommissioned wind turbine blade powder, 7 parts vinyltriethoxysilane, 15 parts polymethylhydrosiloxane, 90 parts n-hexane + isopropanol (volume ratio 1:1), 2 parts platinum catalyst, 10 parts nano titanium dioxide, 400 parts anhydrous ethanol, and 7 parts water.

[0137] Specifically, the preparation steps of a superhydrophobic material based on decommissioned wind turbine blade powder are mostly the same as those in Example 1, except that after heat treatment, the decommissioned wind turbine blade powder is cooled to room temperature and then placed in a planetary ball mill for crushing and refining to 800 mesh; and the slurry is dried to constant weight and then ground to a superhydrophobic material of 800 mesh.

[0138] A concrete containing a superhydrophobic material comprises, by weight, the following components: 300 parts cement, 1020 parts natural coarse aggregate, 660 parts natural sand, 15 parts superhydrophobic material, 1 part water-reducing agent, and 150 parts water.

[0139] The cement used is PO 42.5 ordinary Portland cement with an average particle size of 15.66 μm and a 28-day compressive strength of 48.6 MPa; the natural coarse aggregate is 5-20 mm natural crushed stone aggregate with an apparent density of 2658 kg / m³. 3 The bulk density is 1457 kg / m³. 3 The fineness modulus of the natural sand is 2.9, and the average particle size is 0.37 mm. The water-reducing agent is a high-performance polycarboxylate water-reducing agent with a water reduction rate of 26%. The water is tap water supplied to the laboratory.

[0140] Specifically, the preparation of a concrete containing superhydrophobic materials is carried out in accordance with the steps of Example 1.

[0141] Example 7

[0142] A superhydrophobic material based on decommissioned wind turbine blade powder is compounded from the following raw materials in parts by weight: 100 parts decommissioned wind turbine blade powder, 7 parts vinyltriethoxysilane, 15 parts polymethylhydrosiloxane, 90 parts n-hexane + isopropanol (volume ratio 1:1), 2 parts platinum catalyst, 10 parts nano titanium dioxide, 400 parts anhydrous ethanol, and 7 parts water.

[0143] Specifically, the preparation steps of a superhydrophobic material based on decommissioned wind turbine blade powder are mostly the same as those in Example 1, except that after heat treatment, the decommissioned wind turbine blade powder is cooled to room temperature and then placed in a planetary ball mill for crushing and refining to 300 mesh; and the slurry is dried to constant weight and then ground to a superhydrophobic material of 300 mesh.

[0144] A concrete containing a superhydrophobic material comprises, by weight, the following components: 300 parts cement, 1020 parts natural coarse aggregate, 660 parts natural sand, 15 parts superhydrophobic material, 1 part water-reducing agent, and 150 parts water.

[0145] The cement used is PO 42.5 ordinary Portland cement with an average particle size of 15.66 μm and a 28-day compressive strength of 48.6 MPa; the natural coarse aggregate is 5-20 mm natural crushed stone aggregate with an apparent density of 2658 kg / m³. 3 The bulk density is 1457 kg / m³. 3 The fineness modulus of the natural sand is 2.9, and the average particle size is 0.37 mm. The water-reducing agent is a high-performance polycarboxylate water-reducing agent with a water reduction rate of 26%. The water is tap water supplied to the laboratory.

[0146] Specifically, the preparation of a concrete containing superhydrophobic materials is carried out in accordance with the steps of Example 1.

[0147] Example 8

[0148] A superhydrophobic material based on decommissioned wind turbine blade powder is compounded from the following raw materials in parts by weight: 100 parts decommissioned wind turbine blade powder, 7 parts vinyltriethoxysilane, 5 parts polymethylhydrosiloxane, 90 parts n-hexane + isopropanol (volume ratio 1:1), 2 parts platinum catalyst, 10 parts nano titanium dioxide, 400 parts anhydrous ethanol, and 7 parts water.

[0149] Specifically, the preparation of a superhydrophobic material based on decommissioned wind turbine blade powder is carried out according to the steps of Example 1.

[0150] A concrete containing a superhydrophobic material comprises, by weight, the following components: 300 parts cement, 1020 parts natural coarse aggregate, 660 parts natural sand, 15 parts superhydrophobic material, 1 part water-reducing agent, and 150 parts water.

[0151] The cement used is PO 42.5 ordinary Portland cement with an average particle size of 15.66 μm and a 28-day compressive strength of 48.6 MPa; the natural coarse aggregate is 5-20 mm natural crushed stone aggregate with an apparent density of 2658 kg / m³. 3 The bulk density is 1457 kg / m³. 3 The fineness modulus of the natural sand is 2.9, and the average particle size is 0.37 mm. The water-reducing agent is a high-performance polycarboxylate water-reducing agent with a water reduction rate of 26%. The water is tap water supplied to the laboratory.

[0152] Specifically, the preparation of a concrete containing superhydrophobic materials is carried out in accordance with the steps of Example 1.

[0153] Example 9

[0154] A superhydrophobic material based on decommissioned wind turbine blade powder is compounded from the following raw materials in parts by weight: 100 parts decommissioned wind turbine blade powder, 7 parts vinyltriethoxysilane, 25 parts polymethylhydrosiloxane, 90 parts n-hexane + isopropanol (volume ratio 1:1), 2 parts platinum catalyst, 10 parts nano titanium dioxide, 400 parts anhydrous ethanol, and 7 parts water.

[0155] Specifically, the preparation of a superhydrophobic material based on decommissioned wind turbine blade powder is carried out according to the steps of Example 1.

[0156] A concrete containing a superhydrophobic material comprises, by weight, the following components: 300 parts cement, 1020 parts natural coarse aggregate, 660 parts natural sand, 15 parts superhydrophobic material, 1 part water-reducing agent, and 150 parts water.

[0157] The cement used is PO 42.5 ordinary Portland cement with an average particle size of 15.66 μm and a 28-day compressive strength of 48.6 MPa; the natural coarse aggregate is 5-20 mm natural crushed stone aggregate with an apparent density of 2658 kg / m³.3 The bulk density is 1457 kg / m³. 3 The fineness modulus of the natural sand is 2.9, and the average particle size is 0.37 mm. The water-reducing agent is a high-performance polycarboxylate water-reducing agent with a water reduction rate of 26%. The water is tap water supplied to the laboratory.

[0158] Specifically, the preparation of a concrete containing superhydrophobic materials is carried out in accordance with the steps of Example 1.

[0159] Example 10

[0160] A superhydrophobic material based on decommissioned wind turbine blade powder is compounded from the following raw materials in parts by weight: 100 parts decommissioned wind turbine blade powder, 7 parts vinyltriethoxysilane, 15 parts polymethylhydrosiloxane, 90 parts n-hexane + isopropanol (volume ratio 1:1), 2 parts platinum catalyst, 5 parts nano titanium dioxide, 400 parts anhydrous ethanol, and 7 parts water.

[0161] Specifically, the preparation of a superhydrophobic material based on decommissioned wind turbine blade powder is carried out according to the steps of Example 1.

[0162] A concrete containing a superhydrophobic material comprises, by weight, the following components: 300 parts cement, 1020 parts natural coarse aggregate, 660 parts natural sand, 15 parts superhydrophobic material, 1 part water-reducing agent, and 150 parts water.

[0163] The cement used is PO 42.5 ordinary Portland cement with an average particle size of 15.66 μm and a 28-day compressive strength of 48.6 MPa; the natural coarse aggregate is 5-20 mm natural crushed stone aggregate with an apparent density of 2658 kg / m³. 3 The bulk density is 1457 kg / m³. 3 The fineness modulus of the natural sand is 2.9, and the average particle size is 0.37 mm. The water-reducing agent is a high-performance polycarboxylate water-reducing agent with a water reduction rate of 26%. The water is tap water supplied to the laboratory.

[0164] Specifically, the preparation of a concrete containing superhydrophobic materials is carried out in accordance with the steps of Example 1.

[0165] Example 11

[0166] A superhydrophobic material based on decommissioned wind turbine blade powder is compounded from the following raw materials in parts by weight: 70 parts decommissioned wind turbine blade powder, 4 parts vinyltriethoxysilane, 10 parts polymethylhydrosiloxane, 80 parts n-hexane + isopropanol (volume ratio 1:1), 1 part platinum catalyst, 5 parts nano titanium dioxide, 300 parts anhydrous ethanol, and 4 parts water.

[0167] Specifically, the preparation of a superhydrophobic material based on decommissioned wind turbine blade powder is carried out according to the steps of Example 1.

[0168] A concrete containing a superhydrophobic material comprises, by weight, the following components: 250 parts cement, 960 parts natural coarse aggregate, 630 parts natural sand, 6 parts superhydrophobic material, 0.7 parts water-reducing agent, and 130 parts water.

[0169] The cement used is PO 42.5 ordinary Portland cement with an average particle size of 15.66 μm and a 28-day compressive strength of 48.6 MPa; the natural coarse aggregate is 5-20 mm natural crushed stone aggregate with an apparent density of 2658 kg / m³. 3 The bulk density is 1457 kg / m³. 3 The fineness modulus of the natural sand is 2.9, and the average particle size is 0.37 mm. The water-reducing agent is a high-performance polycarboxylate water-reducing agent with a water reduction rate of 26%. The water is tap water supplied to the laboratory.

[0170] Specifically, the preparation of a concrete containing superhydrophobic materials is carried out in accordance with the steps of Example 1.

[0171] Example 12

[0172] A superhydrophobic material based on decommissioned wind turbine blade powder is compounded from the following raw materials in parts by weight: 130 parts decommissioned wind turbine blade powder, 10 parts vinyltriethoxysilane, 25 parts polymethylhydrosiloxane, 100 parts n-hexane + isopropanol (volume ratio 1:1), 3 parts platinum catalyst, 15 parts nano titanium dioxide, 500 parts anhydrous ethanol, and 10 parts water.

[0173] Specifically, the preparation of a superhydrophobic material based on decommissioned wind turbine blade powder is carried out according to the steps of Example 1.

[0174] A concrete containing a superhydrophobic material comprises, by weight, the following components: 350 parts cement, 1080 parts natural coarse aggregate, 690 parts natural sand, 24 parts superhydrophobic material, 1.3 parts water-reducing agent, and 170 parts water.

[0175] The cement is PO 42.5 ordinary Portland cement with an average particle size of 15.66 μm and a 28-day compressive strength of 48.6 MPa; the coarse aggregate is 5-20 mm natural crushed stone aggregate with an apparent density of 2658 kg / m³. 3 The bulk density is 1457 kg / m³. 3 The fineness modulus of the natural sand is 2.9, and the average particle size is 0.37 mm. The water-reducing agent is a high-performance polycarboxylate water-reducing agent with a water reduction rate of 26%. The water is tap water supplied to the laboratory.

[0176] Specifically, the preparation of a concrete containing superhydrophobic materials is carried out in accordance with the steps of Example 1.

[0177] Comparative Example 1

[0178] Compared with Example 1, the heat treatment of the decommissioned wind turbine blades in step ① is omitted in the preparation process of the superhydrophobic material.

[0179] Comparative Example 2

[0180] Compared to Example 1, vinyltriethoxysilane was replaced with an equal mass of aluminate coupling agent.

[0181] Comparative Example 3

[0182] Compared to Example 1, the addition of vinyltriethoxysilane was omitted.

[0183] Comparative Example 4

[0184] Compared to Example 1, the addition of n-hexane and isopropanol was omitted.

[0185] Comparative Example 5

[0186] Compared to Example 1, polymethylhydrosiloxane was replaced with an equal mass of stearic acid.

[0187] Comparative Example 6

[0188] Compared to Example 1, the addition of polymethylhydrosiloxane was omitted in the preparation of the superhydrophobic material, but the same mass of polymethylhydrosiloxane as in Example 1 was added separately in the concrete preparation process.

[0189] Comparative Example 7

[0190] Compared to Example 1, the addition of polymethylhydrosiloxane was omitted.

[0191] Comparative Example 8

[0192] Compared to Example 1, the addition of superhydrophobic materials was omitted, but polymethylhydrosiloxane of the same mass as in Example 1 was added separately during the concrete preparation process.

[0193] Comparative Example 9

[0194] Compared to Example 1, nano-titanium dioxide was replaced with an equal mass of nano-silicon dioxide.

[0195] Comparative Example 10

[0196] Compared to Example 1, the addition of nano-titanium dioxide was omitted.

[0197] Comparative Example 11

[0198] Compared to Example 1, the superhydrophobic material in the hydrophobic concrete is replaced by decommissioned wind turbine blade powder.

[0199] Comparative Example 12

[0200] Compared to Example 1, the superhydrophobic material in the hydrophobic concrete does not contain decommissioned wind turbine blade powder; it is simply a mixture of other components of the superhydrophobic material added to the concrete.

[0201] The properties of the hydrophobic concrete prepared in each embodiment and comparative example were tested, including the following performance testing methods:

[0202] (1) Water absorption performance test: The method specified in the "Test Procedure for Hydraulic Concrete" (SL 352-2020) was adopted, and the results are shown in Table 1.

[0203] (2) Mechanical performance test: The method specified in the "Standard for Test Method of Mechanical Properties of Ordinary Concrete" (GB / T 50081-2019) was adopted, and the results are shown in Table 1.

[0204] (3) Freeze-thaw performance test: The method specified in the "Standard for Test Methods of Long-term Performance and Durability of Ordinary Concrete" (GB / T50082-2009) was adopted, and the results are shown in Table 1.

[0205] (4) Water contact angle test: The water droplet method was used to test the contact angle of the concrete contact surface using a contact angle measuring instrument. The results are shown in Table 2.

[0206] (5) Photodegradation test: In a closed reaction chamber, the concrete specimen was placed under an irradiance of 10 W·m -2 Under a light source, a constant flow rate (1.5 L·min) is introduced. -1 The NO gas concentration (1.5 ppm) was measured at a humidity of 50%. The outlet gas concentration was monitored in real time using a NO analyzer. The NO degradation efficiency formula is shown in (2), and the results are shown in Table 2.

[0207]

[0208] in, η Indicates NO degradation efficiency. C 0 represents the initial NO concentration. C m This indicates the NO concentration after illumination.

[0209] (6) De-icing performance test: A 20mm×20mm×20mm ice block was formed on the surface of the concrete sample. The sample was then fixed laterally with the side of the ice block facing upwards. A thrust probe was used to apply pressure to the center of the side of the ice block at a constant rate, and the peak thrust when it detached from the sample was recorded. The results are shown in Table 2.

[0210] Table 1. 48-hour water absorption rate, 28-day compressive strength, and frost resistance grade of hydrophobic concrete prepared in each embodiment and comparative example.

[0211]

[0212] Table 1 shows the test results of the impermeability, mechanical properties, and durability of the hydrophobic concretes of Examples 1-12 and Comparative Examples 1-12, including 48-hour water absorption rate, 28-day compressive strength, and frost resistance grade. The results indicate that, due to the use of superhydrophobic materials based on decommissioned wind turbine blade powder, the hydrophobic concretes prepared in each example have relatively low water absorption rates, significantly higher 28-day compressive strengths than the comparative examples, and excellent durability. Specifically, Example 1 has a 48-hour water absorption rate of 3.47%, a 28-day compressive strength of 37.6 MPa, and a frost resistance grade of F325.

[0213] Table 2. Water contact angle, NO degradation rate, and maximum de-icing force of hydrophobic concrete prepared in each embodiment and comparative example.

[0214]

[0215] Table 2 shows the test results of water contact angle, NO degradation efficiency, and maximum de-icing force of the hydrophobic concrete in Examples 1-12 and Comparative Examples 1-12. The results show that, due to the use of superhydrophobic decommissioned wind turbine blade powder, Example 1 has a water contact angle of 138.3°, a NO degradation efficiency of 93.4%, and a maximum de-icing force of 57.9 N.

[0216] Based on the water absorption rate, compressive strength, frost resistance, water contact angle, NO degradation rate, and maximum de-icing force of the hydrophobic concrete in the examples and comparative examples, it was observed that the superhydrophobic material used in Example 1 can significantly improve the comprehensive performance of concrete, specifically by synergistic enhancement of impermeability, mechanical properties, and durability, and possessing multiple functions such as self-cleaning, pollutant degradation, and anti-icing.

[0217] Specifically, compared with Example 1, the superhydrophobic materials prepared in Examples 2 and 3 showed a slight decrease in improving the overall performance of concrete. The main reason is that in Example 2, the steric hindrance of propylenetrimethoxysilane was slightly greater, potentially resulting in lower reactivity, and in Example 3, polymethylsiloxane could only physically coat nano-titanium dioxide. In Example 4, due to the relatively small amount of retired wind turbine blade powder, the total amount of hydrophobic framework was insufficient, making it difficult to construct complete and dense microscopic hydrophobic structural units. In Example 5, due to the high amount of retired wind turbine blade powder, the modifier coverage per unit surface area was insufficient, leading to uneven surface modification and decreased consistency of the microscopic rough structure. In Examples 6 and 7, the particle size of the decommissioned wind turbine blade powder was too large, resulting in a reduced specific surface area and insufficient active sites for reaction with polymethylhydrosiloxane, leading to inadequate surface modification and an incomplete superhydrophobic material structure. In Example 8, the hydrophobic modification of the decommissioned wind turbine blade powder was incomplete due to insufficient polymethylhydrosiloxane dosage. In Example 9, excessive polymethylhydrosiloxane dosage may have resulted in weak binding through physical adsorption, failing to further enhance the hydrophobicity of the modified decommissioned wind turbine blade powder. In Example 10, insufficient nano-titanium dioxide dosage made it difficult to effectively construct a micro-nano composite rough structure on the powder surface, reducing the superhydrophobic performance and its photocatalytic degradation ability for pollutants. Overall, Examples 4-10 deviated from the optimal range of key material parameters, failing to find the best balance between the specific surface area of ​​the powder and the amount of modifier, thus failing to form a superhydrophobic material with the best anti-permeability and functionality. Example 11, due to insufficient superhydrophobic material content, failed to form a continuous hydrophobic network, resulting in limited water-blocking effect and minimal improvement in impermeability. In Example 12, excessive superhydrophobic material content interfered with cement hydration, deteriorated the microstructure, weakened interfacial adhesion, and reduced concrete strength. Comparative Examples 1-12, by omitting or replacing the raw materials of the superhydrophobic material described in this invention, failed to achieve satisfactory practical application results.

[0218] In summary, this invention successfully constructs a functional material with both superhydrophobic and photocatalytic properties by combining retired wind turbine blade powder with functional components such as siloxane modifiers and nano-titanium dioxide. When introduced into concrete, it can improve impermeability, frost resistance, and mechanical properties, while also endowing the structural surface with synergistic functions such as self-cleaning, pollutant degradation, and anti-icing. This provides a reliable technical path for the high-value utilization of retired wind turbine blades and the green preparation of high-performance concrete.

[0219] The above description of the embodiments is provided to enable those skilled in the art to understand and use the present invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A superhydrophobic material based on decommissioned wind turbine blade powder, characterized in that, The raw material components include the following parts by weight: 60-150 parts of decommissioned wind turbine blade powder 2-15 parts of coupling agent, 1-50 parts of siloxane modifier 3-20 parts of nano titanium dioxide 50-150 parts of an alkanol mixture, Catalyst 0.5~5 parts, 100-800 parts of anhydrous ethanol 2-15 parts water; The alkanol mixture was obtained by mixing n-hexane and isopropanol in a volume ratio of 1:

1. The catalyst is a noble metal catalyst; The decommissioned wind turbine blade powder is obtained by pre-treatment, crushing, grinding, resin removal and grading of decommissioned wind turbine blades. The resin removal methods include heat treatment, flocculation or electrostatic separation. The superhydrophobic material is obtained by ultrasonically dispersing decommissioned wind turbine blade powder in anhydrous ethanol, followed by the sequential addition of water, coupling agent, alkanol mixture, catalyst, siloxane modifier, and nano-titanium dioxide for composite reaction.

2. The superhydrophobic material based on decommissioned wind turbine blade powder according to claim 1, characterized in that, When removing resin from the powder of the decommissioned wind turbine blades by heat treatment, the heat-treated powder is cooled to room temperature and then ground to a particle size of 200-10000 mesh. The heat treatment method is as follows: the decommissioned wind turbine blade products, after pretreatment, crushing and grinding, are placed in a furnace containing inert gas at a temperature of 400~700℃ for heat treatment for 0.5~2 hours to remove resin.

3. The superhydrophobic material based on decommissioned wind turbine blade powder according to claim 2, characterized in that, The grinding is carried out by high-speed mechanical crushing, ball milling or air jet milling. When ball milling is used, the rotation speed of the ball mill is 800~1200 r / min and the grinding time is 1~4 hours. The fine particle size of the grinding is 300~1200 mesh.

4. The superhydrophobic material based on decommissioned wind turbine blade powder according to claim 1, characterized in that, The raw material components of the superhydrophobic material based on decommissioned wind turbine blade powder are as follows by weight: 70-130 parts of decommissioned wind turbine blade powder, 4-10 parts of coupling agent, 5-25 parts of siloxane modifier, 5-15 parts of nano titanium dioxide 80-100 parts of an alkanol mixture, 1-3 parts catalyst 300-500 parts of anhydrous ethanol 4-10 parts water.

5. A superhydrophobic material based on decommissioned wind turbine blade powder according to any one of claims 1 to 4, characterized in that, The coupling agent is selected from any one or a mixture of one or more of silanes, titanates, zirconates, and aluminum-titanium composite coupling agents; the silane coupling agent is specifically selected from any one or a mixture of one or more of vinyltriethoxysilane, propenyltrimethoxysilane, and 3-aminopropyltriethoxysilane. The siloxane modifier is selected from any one or a mixture of more than one of polymethylhydrosiloxane, polydimethylsiloxane, polydiethylsiloxane, methyltrimethoxysilane, and hexadecyltrimethoxysilane. The catalyst is a platinum catalyst; The nano-titanium dioxide is commercially available nano-titanium dioxide with a particle size of 20~40nm.

6. A method for preparing a superhydrophobic material based on decommissioned wind turbine blade powder as described in any one of claims 1 to 5, characterized in that, include: First, the powder material of the retired wind turbine blade is ultrasonically dispersed in anhydrous ethanol; then, water and coupling agent are added for surface pretreatment; then, an alkanol mixture is added, followed by the sequential addition of a catalyst and a siloxane modifier; finally, a nano-titanium dioxide suspension is added for grafting and composite reaction. After cleaning, drying and grinding to a certain fineness, a superhydrophobic material with both superhydrophobic and photocatalytic functions can be obtained. The fineness of the superhydrophobic material is 300~1200 mesh.

7. The preparation method according to claim 6, characterized in that, Specifically, the following steps are included: (1) The retired wind turbine blade powder was added to anhydrous ethanol and ultrasonically treated to disperse it fully, according to a ratio of 1:3 between the mass / g of the retired wind turbine blade powder and the volume / mL of anhydrous ethanol, to obtain solution A; the nano titanium dioxide was added to the remaining anhydrous ethanol and ultrasonically treated to obtain a uniform nano titanium dioxide suspension, which was denoted as solution B. The ultrasonic frequencies are all 20~60kHz, and the ultrasonic processing times are all 5~20min. (2) Add water and silane coupling agent dropwise to solution A obtained in step (1) at a constant rate of 1-3 drops / second while stirring. After the addition is complete, continue stirring at room temperature for 5-20 minutes. Then add an alkanol mixture to it. Add catalyst and siloxane modifier dropwise at a constant rate of 1-3 drops / second while stirring. After the addition is complete, stir at 40-80℃ for 5-20 minutes to obtain mixture C. (3) Slowly add the solution B obtained in step (1) to the mixture C in step (2), and stir and react at 40~80℃ for 10~30 min to obtain a slurry; (4) Dry the slurry obtained in step (3) to constant weight, and then grind it to 300~1200 mesh to obtain a superhydrophobic material with active glass fiber as the skeleton, uniformly composited nano titanium dioxide on the surface and modified by a long chain siloxane layer.

8. A hydrophobic concrete comprising the superhydrophobic material according to any one of claims 1 to 5, characterized in that, The raw material components include the following parts by weight: 200-400 parts cement 860-1140 parts of natural coarse aggregate, 600-740 parts natural sand 5-40 parts of superhydrophobic material Water-reducing agent 0.5~2 parts, 120-200 parts water.

9. The hydrophobic concrete according to claim 8, characterized in that, The raw material components of the hydrophobic concrete are as follows by weight: 250-350 parts cement 960-1080 parts of natural coarse aggregate, 630-690 parts natural sand 6-24 parts of superhydrophobic material Water-reducing agent 0.7~1.3 parts, 130-170 parts water; The cement is PO 42.5 ordinary Portland cement with an average particle size of 10~34μm and a 28-day compressive strength of 44.6~51.2MPa; The coarse aggregate is 5-20mm natural crushed stone aggregate with an apparent density of 2600-2800 kg / m³. 3 The bulk density is 1410~1630 kg / m³ 3 ; The fineness modulus of the natural sand is 2.4~3.0, and the average particle size is 0.30~0.60mm; The water-reducing agent is a polycarboxylate high-performance water-reducing agent with a water reduction rate of 22% to 28%.

10. A method for preparing the hydrophobic concrete according to claim 8 or 9, characterized in that, Includes the following steps: (1) Take samples of natural coarse aggregate and natural sand according to the component content in the mix proportion, and pour them into the concrete mixer in sequence and dry mix for 0.5~2 minutes; (2) Take samples of cement and superhydrophobic material according to the component content in the mix proportion, mechanically stir for 0.5 to 2 minutes until they are evenly mixed to form a premix, and then add it to the concrete mixer and dry mix for 0.5 to 3 minutes; (3) Take samples of water and water-reducing agent according to the component content in the ratio, pre-stir in a container for 0.5 to 2 minutes to form a uniform and stable diluted solution, and then slowly add it to the concrete mixer and stir for 1 to 3 minutes to obtain a hydrophobic fresh concrete mixture. (4) The hydrophobic fresh concrete mixture obtained in step (3) is poured into concrete specimens, then compacted on a vibrating table, and demolded after standing at room temperature for 24 hours. Then it is cured for 28 days under standard curing conditions of 20℃±2℃ and relative humidity above 95% to obtain the hydrophobic concrete.

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