Alkali-resistant materials and alkali-resistant glass fibers, their preparation methods and applications

Abstract

This invention relates to the field of industrial waste recycling, and discloses an alkali-resistant material and alkali-resistant glass fiber, their preparation method, and applications. The alkali-resistant material is a composite oxide containing Ba, Ti, and Si; the composite oxide contains BaO, TiO2, and SiO2; wherein the molar ratio of BaO, TiO2, and SiO2 is 0.4-4:0.6-8:1. This alkali-resistant material exhibits excellent alkali resistance. When combined with composite materials from waste wind turbine generators, the resulting alkali-resistant glass fiber shows significantly improved alkali resistance and low cost, making it suitable for large-scale preparation of glass fiber reinforced cementitious materials.

Description

Technical Field

[0001] This invention relates to the field of industrial waste recycling, specifically to an alkali-resistant material and alkali-resistant glass fiber, their preparation methods, and applications. Background Technology

[0002] Composite materials for wind turbine generators mainly include wind turbine blades, nacelle covers, and fairings. The main material for wind turbine blades is a thermosetting composite material reinforced with glass fiber and epoxy resin, primarily containing glass fiber and epoxy resin. The blade shell and web are mainly constructed using a fiber composite "sandwich" laminate structure. The nacelle cover and fairing are thermosetting composite materials reinforced with glass fiber and unsaturated polyester resin, also primarily containing glass fiber and unsaturated polyester resin. With the rapid development of my country's wind power industry, a large number of wind turbine generators have reached the end of their service life and are facing mass decommissioning in recent years. However, as thermosetting composite materials, the waste wind turbine blades, nacelle covers, and fairings have irreversible chemical properties, making their recycling and reuse extremely difficult. Traditional methods for disposing of waste wind turbine composite materials typically involve landfilling and incineration. However, these practices consume significant land resources, cause serious groundwater and air pollution, and fail to fully utilize the residual mechanical properties and value of the composite materials. Facing the large number of decommissioned or damaged wind turbine composite materials in the future, their resource recovery and high-value reuse have become a widely discussed and challenging issue in the industry. Therefore, it is of great significance to develop a low-cost, high-efficiency method for recycling composite materials from waste wind turbine units and to manufacture high-value-added products that meet performance requirements.

[0003] Currently, there are methods to use waste wind turbine materials in the preparation of cement-based materials. However, when glass fiber is used as a reinforcing material in cement-based materials, the OH groups generated during cement hydration... - It can cause severe chemical erosion of the glass fiber skeleton, resulting in poor durability of glass fiber reinforced cement materials.

[0004] Patent application CN 108298915 A proposes an anti-cracking mortar for exterior wall plastering containing recycled fiberglass fibers, with the mortar containing waste fiberglass materials. However, the above solution only utilizes the alkali resistance provided by the resin coating on the surface of the recycled fiberglass fibers. The resin coating only provides a certain degree of alkali resistance, and since some fiberglass is exposed, its alkali resistance still needs further improvement.

[0005] Patent application CN 115286274 A proposes a method for preparing an alkali-resistant coating for recycled fiberglass. This method uses triethoxysilane to modify nano-zirconia particles, suggesting that the modified nano-zirconia particles adhere to the fiberglass surface, improving the coating's adhesion and thus providing alkali resistance. However, this method introduces nano-sized zirconia particles as the main raw material for the alkali-resistant coating. While nano-zirconia particles possess extremely high chemical stability and can remain stable in harsh environments such as acids and alkalis, they are very expensive (approximately 300 RMB / kg). Using this material as an alkali-resistant coating lacks a basis for large-scale application and does not conform to the principle of resource utilization of recycled materials. Furthermore, the process requires ultrasonic dispersion of the sol solution, making it complex and difficult to scale up industrially. Summary of the Invention

[0006] The purpose of this invention is to overcome the problems of poor alkali resistance when using composite materials from waste wind turbine generators to prepare cement-based materials, and the high cost of materials used to improve the alkali resistance of glass fibers. This invention provides an alkali-resistant material and alkali-resistant glass fiber, as well as their preparation method and application. This alkali-resistant material has excellent alkali resistance, and the alkali-resistant glass fiber obtained after being compounded with composite materials from waste wind turbine generators has significantly improved alkali resistance. Moreover, it is inexpensive and suitable for large-scale preparation of glass fiber reinforced cement-based materials.

[0007] To achieve the above objectives, the present invention provides an alkali-resistant material, wherein the alkali-resistant material is a composite oxide containing Ba, Ti and Si;

[0008] The composite oxide containing Ba, Ti and Si contains BaO, TiO2 and SiO2;

[0009] The molar ratio of BaO, TiO2 and SiO2 is 0.4-4:0.6-8:1.

[0010] Preferably, the particle size of the alkali-resistant material is 30-60 nm.

[0011] A second aspect of the present invention provides a method for preparing the above-mentioned alkali-resistant material, the method comprising the following steps:

[0012] a1. Mix the silicon source, titanium source, barium source, water, organic acid and alcohol solvent evenly;

[0013] a2. Heat and stir the material obtained in step a1 until it reaches a sol-gel state, then dry it and calcine it.

[0014] The molar ratio of barium source, titanium source and silicon source is 0.4-4:0.6-8:1, where the weight of barium source and titanium source is based on metal element, and the weight of silicon source is based on silicon element.

[0015] Preferably, the calcination conditions include: a temperature of 400-500℃ and a time of 1-5 hours.

[0016] A third aspect of the present invention provides an alkali-resistant glass fiber material, which is prepared from raw materials containing a silane coupling agent, a waste wind turbine composite material, an alkali-resistant material, and resin A.

[0017] The weight ratio of silane coupling agent, waste wind turbine composite material, alkali-resistant material and resin A is 2:100:0.5-1:0.25-0.5.

[0018] The alkali-resistant material is the aforementioned alkali-resistant material;

[0019] The resin A is selected from one or more of acrylate, unsaturated polyester resin and epoxy resin.

[0020] Preferably, the silane coupling agent comprises one or more of γ-aminopropyltriethoxysilane, 3-glycerolpropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and methyldimethoxysilane;

[0021] Preferably, the composite material of the waste wind turbine contains 60-70 wt% glass fiber and 30-40 wt% resin B, wherein resin B is epoxy resin and / or unsaturated polyester resin.

[0022] A fourth aspect of the present invention provides a method for preparing the above-mentioned alkali-resistant glass fiber material, the method comprising the following steps:

[0023] b1. Cut and crush the composite material of the waste wind turbine to obtain short-cut fibers;

[0024] b2. The silane coupling agent solution is mixed with the chopped fibers and reacted to obtain silane-modified chopped fibers;

[0025] b3. The alcohol solution containing resin A, the alkali-resistant material, the surfactant solution and the silane-modified chopped fibers are mixed and reacted to obtain the alkali-resistant glass fiber material.

[0026] The alkali-resistant material is the aforementioned alkali-resistant material.

[0027] Preferably, the weight ratio of silane coupling agent, waste wind turbine composite material, alkali-resistant material and resin A is 2:100:0.5-1:0.25-0.5;

[0028] Preferably, the weight ratio of the alcohol solution containing resin A to the weight of the alkali-resistant material is 10-20:1;

[0029] Preferably, the surfactant concentration in the surfactant solution is 0.01-5% by mass;

[0030] Preferably, the length of the recycled chopped fibers is 5-20 mm and the aspect ratio is 6-10.

[0031] The fifth aspect of the present invention provides the application of the above-mentioned alkali-resistant material or the alkali-resistant material prepared according to the above method, or the above-mentioned alkali-resistant glass fiber or the alkali-resistant glass fiber prepared according to the above method in the preparation of glass fiber reinforced cementitious materials.

[0032] The alkali-resistant material of this invention is a composite oxide formed by chemical bonds between three oxides: BaO, TiO2, and SiO2, exhibiting excellent alkali resistance. In this alkali-resistant material, BaO has a very dense crystal lattice and good chemical stability, resisting alkali corrosion; TiO2 contains Ti... 4+ When subjected to alkali corrosion, it reacts with OH- - The Ti(OH)4 gel is formed through coordination, and a titanium-rich colloidal film is formed on the surface, which prevents further surface erosion. SiO2 is a tetrahedral network forger, which helps to form a dense oxide network, further improving the alkali resistance of the alkali-resistant material. In the alkali-resistant glass fiber obtained by reacting the alkali-resistant material with waste wind turbine composite material, silane coupling agent, and resin A, the alkali-resistant material and resin A tightly encapsulate the exposed glass fiber in the waste wind turbine composite material, improving the alkali resistance of the glass fiber. This facilitates the use of the waste wind turbine composite material in the preparation of glass fiber reinforced cementitious materials, and further realizes the resource reuse of the waste wind turbine composite material, reducing the recycling cost of the waste wind turbine composite material.

[0033] Furthermore, the alkali-resistant material described in this invention is more inexpensive and has excellent performance, making it suitable for large-scale industrial production. In addition, this invention further develops a method for recycling waste wind power composite materials, producing alkali-resistant glass fibers with excellent properties. This provides a cost-effective alkali-resistant fiber material for downstream cement-based materials applications and also realizes the resource-based reuse of waste wind power composite materials. Detailed Implementation

[0034] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0035] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0036] The present invention provides an alkali-resistant material, wherein the alkali-resistant material is a composite oxide containing Ba, Ti and Si; wherein the composite oxide containing Ba, Ti and Si contains BaO, TiO2 and SiO2.

[0037] In the alkali-resistant material of this invention, BaO, TiO2, and SiO2 form a composite oxide through chemical bonding. Furthermore, due to the very dense crystal lattice of BaO, it possesses excellent chemical stability, thus endowing the material with superior alkali resistance. Simultaneously, when the TiO2 in the alkali-resistant material is subjected to alkali corrosion, the Ti... 4+ It can coordinate with OH- to form a Ti(OH)4 gel, forming a titanium-rich colloidal film on the material surface. This film further prevents the material from being corroded and further improves the alkali resistance of the alkali-resistant material. The SiO2 in the alkali-resistant material is a tetrahedral network forger, which helps to form a dense oxide network structure on the surface of the alkali-resistant material, further improving the alkali resistance of the material.

[0038] In a preferred embodiment, the molar ratio of BaO, TiO2 and SiO2 in the alkali-resistant material is 0.4-4:0.6-8:1, preferably 1-4:1-5:1, and more preferably 1-3:1-3:1.

[0039] In a preferred embodiment, to further improve the alkali resistance of the alkali-resistant material, the particle size of the alkali-resistant material is 30-60 nm.

[0040] The present invention further provides a method for preparing the above-mentioned alkali-resistant material, the method comprising the following steps:

[0041] a1. Mix the silicon source, titanium source, barium source, water, organic acid and alcohol solvent evenly;

[0042] a2. Heat and stir the material obtained in step a1 until it reaches a sol-gel state, then dry it and calcine it.

[0043] In a specific implementation, the molar ratio of barium source, titanium source and silicon source is 0.4-4:0.6-8:1, preferably 1-4:1-5:1, and more preferably 1-3:1-3:1, wherein the weight of barium source and titanium source is based on metal elements, and the weight of silicon source is based on silicon elements.

[0044] In a preferred embodiment, the specific process of step a1 includes:

[0045] s1. Mix the silicon source, organic acid, alcohol solvent and water;

[0046] s2. Mix the material obtained in step s1 with the titanium source and alcohol solvent;

[0047] s3. Mix the material obtained in step s2 with the barium source and organic acid, and then mix it with an alcohol solvent.

[0048] In this invention, the alkali-resistant material is prepared using a sol-gel method. By mixing and reacting a barium source, a titanium source, and a silicon source, the resulting alkali-resistant material contains BaO, TiO2, and SiO2, and these three oxides are interconnected to form a stable structure. By controlling the amount of the three oxides, this invention enables the prepared alkali-resistant material to possess excellent alkali resistance.

[0049] In a preferred embodiment, the mass percentage concentration of tetraethyl orthosilicate in the material obtained in step s1 is 1-10%, preferably 3-6%, and more preferably 5%.

[0050] In specific embodiments, the organic acid is a solvent commonly used in the art that can dissolve the silicon source, such as C2-C5 fatty acids and / or citric acid, preferably C2-C5 fatty acids. In this invention, the organic acid used in steps s1 and s3 is the same; the organic acid in both steps needs to be the same substance. For example, when the organic acid used in step s1 is acetic acid, it can be understood that the organic acid used in step s3 is also acetic acid.

[0051] In a specific embodiment, the C2-C5 fatty acid is selected from one or more of acetic acid, propionic acid, butyric acid, valeric acid, succinic acid, and glutaric acid.

[0052] In a preferred embodiment, the C2-C5 fatty acid is selected from acetic acid, propionic acid, butyric acid, or succinic acid.

[0053] In a specific embodiment, in step s1, the mixing method is stirring. The stirring method can be mechanical stirring or glass rod stirring. Preferably, the stirring time is 100-150 minutes.

[0054] In a specific implementation, in step s1, the volume ratio of organic acid, alcohol solvent and water is 1:1:2-4.

[0055] In this invention, the silicon source is an organosilicon source, such as tetraethyl orthosilicate; the titanium source can be an organic titanium source or an inorganic titanium source, preferably an organic titanium source.

[0056] In a preferred embodiment, the organic titanium source is selected from propyl titanate, butyl titanate, or ethyl titanate, more preferably butyl titanate; the inorganic titanium source is selected from titanium tetrachloride and / or titanium oxysulfate.

[0057] In a specific implementation, the amount of alcohol solvent added in step s2 is not limited; it is sufficient to fully dissolve the titanium source.

[0058] In a specific implementation, in step s2, the mixing method is stirring. Preferably, the stirring time is 20-60 minutes.

[0059] In this invention, in step s3, the barium source can be an inorganic barium source or an organic barium source, preferably an organic barium source.

[0060] In a preferred embodiment, the organic barium source is selected from barium acetate, barium propionate, or barium butyrate, preferably barium acetate; the inorganic barium source is selected from barium carbonate or barium nitrate.

[0061] In a specific implementation, the process of mixing the material obtained in step s2 with the barium source and organic acid in step s3 is as follows: the barium source is mixed with the organic acid, and then mixed with the material obtained in step s2. Specifically, when mixing the barium source with the organic acid, the amount of organic acid added is not limited; it is only necessary to fully dissolve the added barium source.

[0062] In a preferred embodiment, the concentration of the barium source in the material obtained in step s3 is 0.4-0.6 mol / L. Specifically, the concentration of the barium source can be 0.4 mol / L, 0.5 mol / L, or 0.6 mol / L.

[0063] In a specific implementation, in step s3, the mixing method is stirring. Preferably, the stirring time is 100-150 minutes.

[0064] In a specific implementation, the alcohol solvent used in steps s1, s2, and s3 is the same; that is, the same fatty alcohol is used in all three steps. For example, when the alcohol solvent used in step s1 is ethanol, ethanol is also required in steps s2 and s3.

[0065] In a preferred embodiment, the alcohol solvent is selected from methanol, ethanol, propanol, butanol, or butanediol.

[0066] In a specific embodiment, in step a2, when the material obtained in step a2 is heated and stirred until it reaches a sol-gel state, the heating temperature is 50-100℃, preferably 60-80℃. Specifically, the heating temperature can be 50℃, 60℃, 70℃, 80℃, 90℃, or 100℃.

[0067] In a preferred embodiment, in step a2, the calcination conditions include: a temperature of 400-500℃, preferably 420-480℃; and a time of 1-5 hours, preferably 1.5-3 hours. Specifically, the calcination temperature can be 400℃, 450℃, or 500℃; and the calcination time can be 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours.

[0068] The present invention further provides an alkali-resistant glass fiber material, which is prepared from raw materials containing a silane coupling agent, a waste wind turbine composite material, the alkali-resistant material and resin A.

[0069] In this invention, the composite material of the spent wind turbine is a composite material containing glass fiber and resin B, wherein resin B is epoxy resin and / or unsaturated polyester resin. The composite material of the spent wind turbine can be one or more of the following: retired or damaged wind turbine blades, spent wind turbine hub covers, and spent wind turbine fairings. In the composite material of the spent wind turbine, the glass fiber and resin are layered and laminated, and the composite material is formed by cross-linking and curing during the manufacturing process. The mass percentage of glass fiber in the composite material is 60-70 wt%, and the content of resin B is 30-40 wt%.

[0070] In the alkali-resistant glass fiber material of this invention, the silane coupling agent has silane oxygen groups (SiOR) and organic functional groups at both ends. The silane oxygen groups are reactive to inorganic substances, while the organic functional groups are reactive or compatible with organic substances. Therefore, when the silane coupling agent is located between the inorganic and organic interfaces, a bonded layer of organic matrix-silane coupling agent-inorganic matrix can be formed. In the alkali-resistant glass fiber material of this invention, resin B in the waste wind turbine composite material can be coupled with the organic functional groups in the silane coupling agent. Simultaneously, the exposed glass fibers in the waste wind turbine composite material, not coated by resin B, easily couple with the silane oxygen groups of the silane coupling agent, thereby achieving modification of the waste wind turbine composite material by the silane coupling agent. Then, the alkali-resistant material is coupled with the silane oxygen groups on the silane coupling agent, and resin A is also coupled simultaneously. Through multiple couplings, the alkali resistance of the waste wind turbine composite material is further improved.

[0071] In this invention, a silane coupling agent is used to modify the composite material of waste wind turbine generators. Then, the alkali-resistant material and resin are reacted with the modified composite material, so that the alkali-resistant material and resin A can effectively encapsulate the waste wind turbine generator material, thereby resisting the corrosion and intrusion of alkaline substances and improving the alkali resistance of the composite material. This facilitates the better application of the composite material in the preparation of glass fiber reinforced cement-based composite materials, realizing the resource utilization of the composite material of waste wind turbine generators, while simultaneously improving the performance of cement-based materials and saving their preparation costs.

[0072] In a preferred embodiment, the silane coupling agent includes one or more of γ-aminopropyltriethoxysilane, 3-glyceropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and methyldimethoxysilane.

[0073] In a specific embodiment, resin A is one or more of acrylate, unsaturated polyester resin and epoxy resin, preferably acrylate.

[0074] In this invention, the weight ratio of silane coupling agent, waste wind turbine composite material, alkali-resistant material and resin A is 2:100:0.5-1:0.25-0.5, preferably 2:100:0.5-0.8:0.25-0.5.

[0075] The present invention further provides a method for preparing the above-mentioned alkali-resistant glass fiber material, the method comprising the following steps:

[0076] b1. Cut and crush the composite material of the waste wind turbine to obtain short-cut fibers;

[0077] b2. The silane coupling agent solution is mixed with the chopped fibers and reacted to obtain silane-modified chopped fibers;

[0078] b3. The alcohol solution containing resin A, the alkali-resistant material, the surfactant solution, and the silane-modified short-cut fibers are mixed and reacted to obtain the alkali-resistant glass fiber material.

[0079] In a specific implementation, the weight ratio of silane coupling agent, waste wind turbine composite material, alkali-resistant material and resin A is 2:100:0.5-1:0.25-0.5, preferably 2:100:0.5-0.8:0.25-0.5.

[0080] In this invention, in step b1, the fragments obtained after cutting and crushing the waste wind turbine composite material are mostly in the form of fiber bundles. Preferably, to further facilitate the subsequent use of the prepared alkali-resistant glass fiber material in the preparation of glass fiber reinforced cementitious materials, the fragments obtained after crushing are sieved to obtain recycled short-cut fibers with a length of 5-20 mm and an aspect ratio of 6-10.

[0081] In a specific embodiment, in step b2, the silane coupling agent solution is obtained by mixing a silane coupling agent with an alcohol solvent and then mixing it with water. The silane coupling agent includes one or more of γ-aminopropyltriethoxysilane, 3-glycerolpropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and methyldimethoxysilane.

[0082] In a preferred embodiment, the mass percentage concentration of the silane coupling agent in the silane coupling agent solution is 15-30%. Specifically, the mass percentage concentration of the silane coupling agent can be 15%, 20%, 25%, or 30%.

[0083] In a preferred embodiment, the weight ratio of alcohol solvent to water in the silane coupling agent solution is 8-10:1.

[0084] In a specific implementation, the alcohol solvent is the same as the alcohol solvent selected in steps s1, s2 and s3.

[0085] In this invention, in step b2, a silane coupling agent is used to perform liquid-solid surface chemical coating modification on the composite material of the waste wind turbine, thereby coating the exposed glass fibers on the surface of the composite material to obtain silane-modified short-cut fibers.

[0086] In a preferred embodiment, the content of the chopped fibers in the reaction raw materials of step b2 is 20-30%.

[0087] In a preferred embodiment, step b3 specifically includes: first mixing an alcohol solution containing resin A with the alkali-resistant material, then mixing it with a surfactant solution, and then reacting the mixed material with the silane-modified chopped fibers to obtain an alkali-resistant glass fiber material.

[0088] In this invention, silane-modified chopped fibers are reacted with the alkali-resistant material, wherein the silanoxy groups in the silane-modified chopped fibers are coupled with the alkali-resistant material, thereby improving the alkali resistance of the waste wind turbine composite material. Furthermore, the resin A in the alcohol solution containing resin A is further coupled with the organic groups contained in the silane-modified chopped fibers, allowing the resin coating to adhere uniformly and densely to the exposed glass fiber surface, further enhancing the performance of the prepared alkali-resistant glass fiber.

[0089] In this invention, using resin A for the reaction allows for better compatibility between the organic and inorganic phases in subsequent reactions, facilitating the reaction process. Resin A is one or more of acrylate, unsaturated polyester resin, and epoxy resin, preferably acrylate.

[0090] In this invention, the dispersibility of the alkali-resistant material is increased by adding a surfactant to prevent the alkali-resistant material from agglomerating. Commonly used surfactants in the art can be used, preferably sodium pyrophosphate and / or disodium ethylenediaminetetraacetate.

[0091] In a preferred embodiment, the surfactant concentration in the solution containing the surfactant is 0.01-5% by mass, preferably 1-3%.

[0092] In a preferred embodiment, the weight ratio of the alcohol solution containing resin A to the alkali-resistant material is 10-20:1. Specifically, the weight ratio of the alcohol solution containing resin A to the alkali-resistant material can be 10:1, 15:1, or 20:1.

[0093] The present invention further provides the application of the above-mentioned alkali-resistant material or the alkali-resistant material prepared according to the above method, or the above-mentioned alkali-resistant glass fiber or the alkali-resistant glass fiber prepared according to the above method in the preparation of glass fiber reinforced cementitious materials.

[0094] The present invention will be described in detail below through embodiments, but the scope of protection of the present invention is not limited thereto.

[0095] The waste wind power composite material used in the following examples and comparative examples is waste wind turbine blades. The waste wind turbine blades contain 70wt% glass fiber and 30wt% epoxy resin, which are obtained by mechanical crushing after the wind farm is scrapped. Unless otherwise specified, the other materials used are conventional commercial products.

[0096] Example 1

[0097] (1) Short fibers with a size of 5-20mm and an aspect ratio of 6-10 are obtained by cutting, crushing and sorting waste wind power composite materials;

[0098] (2) Add the silane coupling agent (γ-aminopropyltriethoxysilane KH550) to ethanol and stir to mix evenly. Then add water to obtain a mixed solution. The mass percentage concentration of the silane coupling agent is 20%, and the weight ratio of ethanol to water is 9:1.

[0099] (3) The material obtained in step (2) is thoroughly stirred and mixed with the chopped fiber to react and obtain silane-modified chopped fiber, wherein the content of chopped fiber in the reactant is 20 wt%.

[0100] (4) Mix tetraethyl orthosilicate with acetic acid, ethanol and water for 120 min until homogeneous. The volume ratio of acetic acid, ethanol and water is 1:1:3.

[0101] (5) Mix the material obtained in step (4) with titanium source (titanium butyl ester) and ethanol for 30 min until homogeneous;

[0102] (6) Dissolve the barium source (barium acetate) in acetic acid, then add the material obtained in step (5) and continue stirring for 120 min to mix evenly. Then add ethanol and mix evenly to make the concentration of barium acetate 0.5 mol / L. The molar ratio of tetraethyl orthosilicate, tetrabutyl titanate and barium acetate is 1:2:2.

[0103] (7) Heat the material obtained in step (6) to 60°C and stir it thoroughly until it becomes a sol-gel, then dry it;

[0104] (8) The dried material was calcined at 450℃ for 2 hours to obtain an alkali-resistant material (wherein the molar ratio of BaO:TiO2:SiO2 is 2:2:1);

[0105] (9) Dissolve acrylate in ethanol to obtain an alcoholic solution of acrylate, then stir and mix it with the alkali-resistant material until the alkali-resistant material is completely dissolved, and then mix it with a sodium pyrophosphate solution with a mass percentage concentration of 0.5%, wherein the weight ratio of the alcoholic solution of acrylate to the weight of the alkali-resistant material is 15:1.

[0106] (10) At a temperature of 60°C, the material obtained in step (9) is mixed with silane-modified short-cut fibers and reacted for 24 hours. After the reaction is completed, the mixture is filtered, the filter residue is washed with water and dried to obtain alkali-resistant glass fiber material.

[0107] The weight ratio of silane coupling agent, waste wind turbine composite material, alkali-resistant material and acrylate is 2:100:0.5:0.25.

[0108] Example 2

[0109] (1) Short fibers with a size of 5-20mm and an aspect ratio of 6-10 are obtained by cutting, crushing and sorting waste wind power composite materials;

[0110] (2) Add the silane coupling agent (3-glycerolpropyltrimethoxysilane KH560) to ethanol and stir to mix evenly. Then add water to obtain a mixed solution. The mass percentage concentration of the silane coupling agent is 20%, and the weight ratio of ethanol to water is 9:1.

[0111] (3) The material obtained in step (2) is thoroughly stirred and mixed with the chopped fiber to react and obtain silane-modified chopped fiber, wherein the content of chopped fiber in the reactant is 20 wt%.

[0112] (4) Mix tetraethyl orthosilicate with acetic acid, ethanol and water for 120 min until homogeneous. The volume ratio of acetic acid, ethanol and water is 1:1:3.

[0113] (5) Mix the material obtained in step (4) with titanium source (titanium butyl ester) and ethanol for 30 min until homogeneous;

[0114] (6) Dissolve the barium source (barium acetate) in acetic acid, then add the material obtained in step (5) and continue stirring for 120 min to mix evenly. Then add ethanol and mix evenly to make the concentration of barium acetate 0.5 mol / L. The molar ratio of tetraethyl orthosilicate, tetrabutyl titanate and barium acetate is 1:3:2.

[0115] (7) Heat the material obtained in step (6) to 60°C and stir it thoroughly until it becomes a sol-gel, then dry it;

[0116] (8) The dried material was calcined at 450℃ for 2 hours to obtain an alkali-resistant material (wherein the molar ratio of BaO:TiO2:SiO2 is 2:3:1);

[0117] (9) Dissolve acrylate in ethanol to obtain an alcoholic solution of acrylate, then stir and mix it with the alkali-resistant material until the alkali-resistant material is completely dissolved, and then mix it with a 0.5% (w / w) disodium ethylenediaminetetraacetate solution. The weight ratio of the alcoholic solution of acrylate to the weight of the alkali-resistant material is 15:1.

[0118] (10) At a temperature of 60°C, the material obtained in step (9) is mixed with silane-modified short-cut fibers and reacted for 24 hours. After the reaction is completed, the mixture is filtered, the filter residue is washed with water and dried to obtain alkali-resistant glass fiber material.

[0119] The weight ratio of silane coupling agent, waste wind turbine composite material, alkali-resistant material and acrylate is 2:100:0.6:0.25.

[0120] Example 3

[0121] (1) Short fibers with a size of 5-20mm and an aspect ratio of 6-10 are obtained by cutting, crushing and sorting waste wind power composite materials;

[0122] (2) Add the silane coupling agent (3-glycerolpropyltrimethoxysilane KH560) to ethanol and stir to mix evenly. Then add water to obtain a mixed solution. The mass percentage concentration of the silane coupling agent is 20%, and the weight ratio of ethanol to water is 9:1.

[0123] (3) The material obtained in step (2) is thoroughly stirred and mixed with the chopped fiber to react and obtain silane-modified chopped fiber, wherein the content of chopped fiber in the reactant is 20 wt%.

[0124] (4) Mix tetraethyl orthosilicate with acetic acid, ethanol and water for 120 min until homogeneous. The volume ratio of acetic acid, ethanol and water is 1:1:3.

[0125] (5) Mix the material obtained in step (4) with titanium source (titanium butyl ester) and ethanol for 30 min until homogeneous;

[0126] (6) Dissolve the barium source (barium acetate) in acetic acid, then add the material obtained in step (5) and continue stirring for 120 min to mix evenly. Then add ethanol and mix evenly to make the concentration of barium acetate 0.5 mol / L. The molar ratio of tetrabutyl titanate, barium acetate and tetraethyl orthosilicate is 2:2:1.

[0127] (7) Heat the material obtained in step (6) to 60°C and stir it thoroughly until it becomes a sol-gel, then dry it;

[0128] (8) The dried material was calcined at 450℃ for 2 hours to obtain an alkali-resistant material (wherein the molar ratio of BaO:TiO2:SiO2 is 2:2:1);

[0129] (9) Dissolve acrylate in ethanol to obtain an alcoholic solution of acrylate, then stir and mix it with the alkali-resistant material until the alkali-resistant material is completely dissolved, and then mix it with a sodium pyrophosphate solution with a mass percentage concentration of 0.5%, wherein the weight ratio of the alcoholic solution of acrylate to the weight of the alkali-resistant material is 15:1.

[0130] (10) At a temperature of 60°C, the material obtained in step (9) is mixed with silane-modified short-cut fibers and reacted for 24 hours. After the reaction is completed, the mixture is filtered, the filter residue is washed with water and dried to obtain alkali-resistant glass fiber material.

[0131] The weight ratio of silane coupling agent, waste wind turbine composite material, alkali-resistant material and acrylate is 2:100:0.8:0.25.

[0132] Example 4

[0133] (1) Short fibers with a size of 5-20mm and an aspect ratio of 6-10 are obtained by cutting, crushing and sorting waste wind power composite materials;

[0134] (2) Add the silane coupling agent (3-glycerolpropyltrimethoxysilane KH560) to ethanol and stir to mix evenly. Then add water to obtain a mixed solution. The mass percentage concentration of the silane coupling agent is 20%, and the weight ratio of ethanol to water is 9:1.

[0135] (3) The material obtained in step (2) is thoroughly stirred and mixed with the chopped fiber to react and obtain silane-modified chopped fiber, wherein the content of chopped fiber in the reactant is 20 wt%.

[0136] (4) Mix tetraethyl orthosilicate with acetic acid, ethanol and water for 120 min until homogeneous. The volume ratio of acetic acid, ethanol and water is 1:1:3.

[0137] (5) Mix the material obtained in step (4) with titanium source (titanium butyl ester) and ethanol for 30 min until homogeneous;

[0138] (6) Dissolve the barium source (barium acetate) in acetic acid, then add the material obtained in step (5) and continue stirring for 120 min to mix evenly. Then add ethanol and mix evenly to make the concentration of barium acetate 0.5 mol / L. The molar ratio of tetraethyl orthosilicate, tetrabutyl titanate and barium acetate is 1:2:2.

[0139] (7) Heat the material obtained in step (6) to 60°C and stir it thoroughly until it becomes a sol-gel, then dry it;

[0140] (8) The dried material is calcined at 450℃ for 2 hours to obtain alkali-resistant material (wherein the molar ratio of BaO:TiO2:SiO2 is 2:2:1);

[0141] (9) Dissolve acrylate in ethanol to obtain an alcoholic solution of acrylate, then stir and mix it with the alkali-resistant material until the alkali-resistant material is completely dissolved, and then mix it with a sodium pyrophosphate solution with a mass percentage concentration of 0.5%, wherein the weight ratio of the alcoholic solution of acrylate to the weight of the alkali-resistant material is 15:1.

[0142] (10) At a temperature of 60°C, the material obtained in step (9) is mixed with silane-modified short-cut fibers and reacted for 24 hours. After the reaction is completed, the mixture is filtered, the filter residue is washed with water and dried to obtain alkali-resistant glass fiber material.

[0143] The content ratio of silane-modified short-cut fiber, alkali-resistant material, silane coupling agent and acrylate is 2:100:0.1:0.25.

[0144] Example 5

[0145] (1) Short fibers with a size of 5-20mm and an aspect ratio of 6-10 are obtained by cutting, crushing and sorting waste wind power composite materials;

[0146] (2) Add the silane coupling agent (3-glycerolpropyltrimethoxysilane KH560) to ethanol and stir to mix evenly. Then add water to obtain a mixed solution. The mass percentage concentration of the silane coupling agent is 20%, and the weight ratio of ethanol to water is 9:1.

[0147] (3) The material obtained in step (2) is thoroughly stirred and mixed with the chopped fiber to react and obtain silane-modified chopped fiber, wherein the content of chopped fiber in the reactant is 20 wt%.

[0148] (4) Mix tetraethyl orthosilicate with acetic acid, ethanol and water for 120 min until homogeneous. The volume ratio of acetic acid, ethanol and water is 1:1:3.

[0149] (5) Mix the material obtained in step (4) with titanium source (titanium butyl ester) and ethanol for 30 min until homogeneous;

[0150] (6) Dissolve the barium source (barium acetate) in acetic acid, then add the material obtained in step (5) and continue stirring for 120 min to mix evenly. Then add ethanol and mix evenly to make the concentration of barium acetate 0.5 mol / L. The molar ratio of tetraethyl orthosilicate, tetrabutyl titanate and barium acetate is 1:2:2.

[0151] (7) Heat the material obtained in step (6) to 60°C and stir it thoroughly until it becomes a sol-gel, then dry it;

[0152] (8) The dried material is calcined at 450℃ for 2 hours to obtain alkali-resistant material (wherein the molar ratio of BaO:TiO2:SiO2 is 2:2:1);

[0153] (9) Dissolve acrylate in ethanol to obtain an alcoholic solution of acrylate, then stir and mix it with alkali-resistant material until the alkali-resistant material is completely dissolved, and then mix it with sodium pyrophosphate solution with a mass percentage concentration of 0.5%, wherein the weight ratio of the alcoholic solution of acrylate to the weight of the alkali-resistant material is 15:1.

[0154] (10) At a temperature of 60°C, the material obtained in step (9) is mixed with silane-modified short-cut fibers and reacted for 24 hours. After the reaction is completed, the mixture is filtered, the filter residue is washed with water and dried to obtain alkali-resistant glass fiber material.

[0155] The content ratio of silane-modified short-cut fiber, alkali-resistant material, silane coupling agent and acrylate is 2:100:1.2:0.25.

[0156] Comparative Example 1

[0157] (1) Short fibers with a size of 5-20mm and an aspect ratio of 6-10 are obtained by cutting, crushing and sorting waste wind power composite materials;

[0158] (2) Add the silane coupling agent (3-glycerolpropyltrimethoxysilane KH560) to ethanol and stir to mix evenly. Then add water to obtain a mixed solution. The mass percentage concentration of the silane coupling agent is 20%, and the weight ratio of ethanol to water is 9:1.

[0159] (3) The material obtained in step (2) is thoroughly stirred and mixed with the chopped fibers to react and obtain silane-modified chopped fibers;

[0160] (4) Mix tetraethyl orthosilicate with acetic acid, ethanol and water for 120 min until homogeneous. The volume ratio of acetic acid, ethanol and water is 1:1:3.

[0161] (5) Dissolve the barium source (barium acetate) in acetic acid solution, then add the material obtained in step (4) and continue stirring for 120 min to mix evenly, then add ethanol and mix evenly; wherein the molar ratio of tetraethyl orthosilicate to barium acetate is 1:2;

[0162] (6) Heat the material obtained in step (5) to 60°C and stir it thoroughly until it becomes a sol-gel, then dry it;

[0163] (7) The dried material was calcined at 450℃ for 2 hours to obtain the material (wherein, BaO:SiO2=0.67:0.33);

[0164] (8) After dissolving the acrylate in ethanol and mixing it evenly, it is then stirred and mixed evenly with the material obtained in step (7), and then mixed evenly with a sodium pyrophosphate solution with a mass percentage concentration of 0.5%; the weight ratio of the ethanol solution of acrylic acid to the weight of the material obtained in step (7) is 15:1.

[0165] (9) At a temperature of 60°C, the material obtained in step (8) is mixed with silane-modified short-cut fibers and reacted for 24 hours. After the reaction is completed, the mixture is filtered, the filter residue is washed with water and dried to obtain alkali-resistant glass fiber material.

[0166] The content ratio of silane-modified short-cut fibers, the material obtained in step (7), silane coupling agent and acrylate is 2:100:0.5:0.25.

[0167] Comparative Example 2

[0168] (1) Short fibers with a size of 5-20mm and an aspect ratio of 6-10 are obtained by cutting, crushing and sorting waste wind power composite materials;

[0169] (2) Add the silane coupling agent (γ-aminopropyltriethoxysilane KH550) to ethanol and stir to mix evenly. Then add water to obtain a mixed solution. The mass percentage concentration of the silane coupling agent is 20%, and the weight ratio of ethanol to water is 9:1.

[0170] (3) The material obtained in step (2) is thoroughly stirred and mixed with the chopped fibers to react and obtain silane-modified chopped fibers;

[0171] (4) Mix tetraethyl orthosilicate with acetic acid, ethanol and water for 120 min until homogeneous. The volume ratio of acetic acid, ethanol and water is 1:1:3.

[0172] (5) Mix the material obtained in step (4) with titanium source (tetrabutyl titanate) and ethanol and stir for 30 min; wherein the molar ratio of tetraethyl orthosilicate to tetrabutyl titanate is 1:2.

[0173] (6) Heat the material obtained in step (5) to 60°C and stir it thoroughly until it becomes a sol-gel, then dry it;

[0174] (7) The dried material was calcined at 450℃ for 2 hours to obtain the material (wherein, TiO2:SiO2=0.67:0.33);

[0175] (8) After dissolving the acrylate in ethanol and mixing it evenly, it is then stirred and mixed evenly with the material obtained in step (7), and then mixed evenly with a sodium pyrophosphate solution with a mass percentage concentration of 0.5%; the weight ratio of the ethanol solution of acrylic acid to the weight of the material obtained in step (7) is 15:1.

[0176] (9) The material obtained in step (8) is mixed with silane-modified short-cut fibers and reacted at a reaction temperature of 60°C for 24 hours to obtain the product.

[0177] The content ratio of silane-modified short-cut fibers, the material obtained in step (7), silane coupling agent and acrylate is 2:100:0.5:0.25.

[0178] Comparative Example 3

[0179] (1) Short fibers with a size of 5-20mm and an aspect ratio of 6-10 are obtained by cutting, crushing and sorting waste wind power composite materials;

[0180] (2) Add the silane coupling agent (γ-aminopropyltriethoxysilane KH550) to ethanol and stir to mix evenly. Then add water to obtain a mixed solution. The mass percentage concentration of the silane coupling agent is 20%, and the weight ratio of ethanol to water is 9:1.

[0181] (3) The material obtained in step (2) is thoroughly stirred and mixed with the chopped fibers to react and obtain silane-modified chopped fibers;

[0182] (4) Mix the titanium source (titanium tetrabutyl ester) and ethanol for 30 min;

[0183] (5) Dissolve the barium source (barium acetate) in acetic acid, then add the material obtained in step (4) and continue stirring for 120 min to mix evenly. Then add ethanol and mix evenly to make the concentration of barium acetate 0.5 mol / L. The molar ratio of tetrabutyl titanate to barium acetate is 1:1.

[0184] (6) Heat the material obtained in step (5) to 60°C and stir it thoroughly until it becomes a sol-gel, then dry it;

[0185] (7) The dried material was calcined at 450℃ for 2 hours to obtain the material (wherein, BaO:TiO2=1:1);

[0186] (8) After dissolving the acrylate in ethanol and mixing it evenly, it is then stirred and mixed evenly with the material obtained in step (7), and then mixed evenly with a sodium pyrophosphate solution with a mass percentage concentration of 0.5%; the weight ratio of the ethanol solution of acrylic acid to the weight of the material obtained in step (7) is 15:1.

[0187] (9) The material obtained in step (8) is mixed with silane-modified short-cut fibers and reacted at a reaction temperature of 60°C for 24 hours to obtain alkali-resistant glass fiber material.

[0188] The content ratio of silane-modified short-cut fiber, the material obtained in step (7), silane coupling agent and resin is 2:100:0.5:0.25.

[0189] Test case

[0190] Test Example 1

[0191] The alkali resistance properties of the alkali-resistant glass fiber materials prepared in Examples 1-5, the products prepared in Comparative Examples 1-3, and untreated waste wind turbine blades were tested.

[0192] Test method: A mixture of 1 mol / L NaOH solution and saturated Ca(OH)2 solution was used as the corrosive medium. The sample to be tested was immersed in the corrosive medium at room temperature for 35 days. The weight loss of the sample was measured every 7 days, and fresh corrosive medium was used to replace the sample every 7 days. The weight loss rate of the sample was recorded each time. The calculation formula is: (weight of sample before corrosion - weight of sample after corrosion) ÷ weight of sample before corrosion × 100%. The results are shown in Table 1.

[0193] Table 1

[0194]

[0195] As can be seen from the results in Table 1, the alkali-resistant glass fiber material prepared by the method described in this invention has excellent alkali resistance, and can better apply waste wind power composite materials to the preparation of glass fiber reinforced cement-based composite materials.

[0196] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. An alkali-resistant glass fiber material, characterized in that, The alkali-resistant glass fiber material is prepared from raw materials containing silane coupling agent, waste wind turbine composite material, alkali-resistant material and resin A; The weight ratio of silane coupling agent, waste wind turbine composite material, alkali-resistant material and resin A is 2:100:0.5-1:0.25-0.

5. The alkali-resistant material is a composite oxide containing Ba, Ti and Si, wherein the composite oxide contains BaO, TiO2 and SiO2, and the molar ratio of BaO, TiO2 and SiO2 is 0.4-4:0.6-8:

1. The resin A is selected from one or more of acrylate, unsaturated polyester resin and epoxy resin; The silane coupling agent is selected from one or more of γ-aminopropyltriethoxysilane, 3-glyceropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane; The composite material of the waste wind turbine contains 60-70 wt% glass fiber and 30-40 wt% resin B, wherein resin B is epoxy resin and / or unsaturated polyester resin.

2. The alkali-resistant glass fiber material according to claim 1, wherein the particle size of the alkali-resistant material is 30-60 nm.

3. The alkali-resistant glass fiber material according to claim 1, characterized in that, The preparation method of the alkali-resistant material includes the following steps: a1. Mix the silicon source, titanium source, barium source, water, organic acid and alcohol solvent evenly; a2. Heat and stir the material obtained in step a1 until it reaches a sol-gel state, then dry it and calcine it. The molar ratio of barium source, titanium source and silicon source is 0.4-4:0.6-8:1, where the weight of barium source and titanium source is based on metal element, and the weight of silicon source is based on silicon element.

4. The alkali-resistant glass fiber material according to claim 3, characterized in that, The heating temperature is 50-100℃.

5. The alkali-resistant glass fiber material according to claim 3, characterized in that, The roasting conditions include: a temperature of 400-500℃ and a time of 1-5 hours.

6. A method for preparing the alkali-resistant glass fiber material according to any one of claims 1-5, characterized in that, The method includes the following steps: b1. Cut and crush the composite material of the waste wind turbine to obtain short-cut fibers; b2. The silane coupling agent solution is mixed with the chopped fibers and reacted to obtain silane-modified chopped fibers; b3. The alcohol solution containing resin A, the alkali-resistant material, the surfactant solution, and the silane-modified chopped fibers are mixed and reacted to obtain the alkali-resistant glass fiber material.

7. The method according to claim 6, characterized in that, The weight ratio of the alcohol solution containing resin A to the weight of the alkali-resistant material is 10-20:

1.

8. The method according to claim 6, characterized in that, In the surfactant solution, the mass percentage concentration of the surfactant is 0.01-5%.

9. The method according to claim 6, characterized in that, The chopped fibers have a length of 5-20 mm and an aspect ratio of 6-10.

10. The method according to claim 6, characterized in that, In step b3, the reaction conditions include a temperature of 40-80°C and a time of 20-30 hours.

11. The use of the alkali-resistant glass fiber material according to any one of claims 1-5 in the preparation of glass fiber reinforced cementitious materials.

Images