Basalt fiber composite material with surface-grown bismuth oxyhalide and preparation method and application thereof

Abstract

This invention provides a basalt fiber composite material with surface-grown bismuth halide, its preparation method, and its application, belonging to the field of basalt fiber. Specifically, it includes using water or low-carbon alcohols as solvents to prepare materials containing Bi. 3+ Solution A and cation K + 、Rb + or Cs + A precursor solution, consisting of a halide ion (solution B), is slowly added to solution A. Cleaned basalt fibers are then subjected to hydrophilic modification using a hydrophilic surfactant solution to obtain hydrophilic basalt fibers. The precursor solution and the hydrophilic basalt fibers are then placed together in a high-pressure reactor to prepare a basalt fiber composite material with bismuth halide grown on its surface. This processing method allows bismuth halide to be grown on the surface of the basalt fiber, and enhances its mechanical properties through ion exchange.

Description

Technical Field

[0001] This invention relates to the field of basalt fiber, specifically to a basalt fiber composite material with bismuth halide grown on its surface, its preparation method, and its application. Background Technology

[0002] Basalt fiber is a high-performance inorganic fiber material made from natural basalt rock through high-temperature melting and drawing. Basalt is a widely distributed volcanic rock on Earth, and after processing, it can be used to produce fibers with excellent properties. Similar to glass fiber, basalt fiber has better mechanical strength, high-temperature resistance, corrosion resistance, and environmental friendliness. Therefore, it has wide applications in fiber-reinforced composites, high-temperature filtration, and sound absorption and noise reduction. However, the mechanical properties of basalt fiber still have room for improvement in some high-strength and high-modulus applications.

[0003] Bismuth oxide (BiOX, X = Cl, Br, I) is a class of bismuth oxides. 3 Layered photocatalytic materials composed of bismuth oxyhalides and halide anions (Cl-, Br-, I-) have shown broad application potential in various fields in recent years, particularly in environmental remediation, energy conversion, and sensors. Loading bismuth oxyhalides onto fibers has become a research hotspot in recent years. How to combine bismuth oxyhalides nanoparticles with photoelectric properties with basalt fibers to obtain basalt fibers with photoelectric functionalities is key to introducing basalt fibers into applications such as environmental remediation and composite materials.

[0004] Currently, some researchers use hydrothermal / solvothermal methods and continuous ion-layer adsorption to load bismuth oxyhalides onto fibers. However, the high temperature and pressure environment of hydrothermal / solvothermal methods can reduce the mechanical properties of the fibers, while continuous ion-layer adsorption methods have drawbacks such as weak bonding between the semiconductor and the fiber, and a cumbersome and time-consuming preparation process. In addition, a large number of ions in the precursor solution cannot be effectively utilized. Therefore, how to improve the recyclability of bismuth oxyhalides through modification, enhance the utilization rate of ions in the precursor solution, and improve the mechanical properties of fibers while growing bismuth oxyhalides on the surface has become an important research topic. Summary of the Invention

[0005] Therefore, to overcome the shortcomings of the prior art, this invention provides a basalt fiber composite material with surface-grown bismuth halide, its preparation method, and its application. Nano-sized bismuth halide particles are directly grown on the surface of basalt fibers using a hydrothermal or solvothermal method, and the mechanical properties of the basalt fibers are improved through ion exchange, thus obtaining a basalt fiber composite material.

[0006] To achieve the above objectives, this invention provides a basalt fiber composite material with surface-grown bismuth halide, its preparation method, and its application, comprising: Step one, using water or a low-carbon alcohol as a solvent, respectively preparing a mixture containing Bi... 3+ Solution A and cation K + 、Rb + or Cs + In step one, solution B, containing halide ions, is stirred for 30–60 min. The molar concentration of solution A is 0.0857–0.2571 mol / L, and the molar concentration of solution B is 0.0857–0.2571 mol / L. The carbon number of the low-carbon alcohol does not exceed 5. In step two, solution B obtained in step one is slowly added to solution A, and stirred for another 30–60 min to obtain a precursor solution. In step three, the cleaned basalt fibers are placed in a hydrophilic surfactant solution and refluxed in a water bath at 60–80 °C for 4–8 h to perform hydrophilic modification, thereby obtaining hydrophilic basalt fibers. In step four, the precursor solution and the hydrophilic basalt fibers are placed together in a high-pressure reactor and kept at 120–180 °C for 4–16 h to prepare a basalt fiber composite material with bismuth halogen oxide grown on its surface.

[0007] In one embodiment, the lower alcohol mentioned in step one is any one of ethanol, ethylene glycol, isopropanol, and glycerol.

[0008] In one embodiment, solution A in step one is prepared using Bi(NO3)3·5H2O, BiCl3, or NaBiO3·2H2O.

[0009] In one embodiment, the solution B in step one is prepared using KI, KBr, KCl, RbI, RbBr, RbCl, CsI, CsBr, or CsCl.

[0010] In one embodiment, the ratio of solution A to solution B in step two is in the range of 1:1 to 1:3.

[0011] In one embodiment, the cleaned basalt fiber described in step three is obtained by cleaning with acetone solution and deionized water.

[0012] In one embodiment, the pressure inside the high-pressure reactor in step four is not less than 0.1 MPa.

[0013] In one embodiment, the tensile strength of the basalt fiber composite material in step four is increased by 5-90%, and the elastic modulus is increased by 5-80%.

[0014] A basalt fiber composite material with bismuth halide grown on its surface, wherein the basalt fiber composite material with bismuth halide grown on its surface is prepared by the method described above.

[0015] Application of a basalt fiber composite material with surface-grown bismuth halide, wherein the surface-grown bismuth halide basalt fiber composite material is used for photocatalytic degradation.

[0016] Compared with existing technologies, the advantages of this invention are: nano-sized bismuth halide particles are directly grown on the surface of basalt fibers using hydrothermal or solvothermal methods to obtain basalt fiber composite materials. Furthermore, during the growth of bismuth halide, the large-radius K0 particles in the precursor solution... + (Rb + or Cs + ) ions and smaller radius Na in basalt fibers + Ions undergo ion exchange under high temperature and high pressure, which further endows basalt fiber composite materials with higher mechanical properties, thereby expanding the application of basalt fibers in environmental remediation, composite materials and other functional properties. Attached Figure Description

[0017] To more clearly illustrate the technical solutions of the embodiments of this application, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 This is a schematic flowchart illustrating the preparation method of basalt fiber composite material in an embodiment of the present invention. Detailed Implementation

[0019] The embodiments of this application will now be described in detail with reference to the accompanying drawings.

[0020] The following specific examples illustrate the implementation of this application. Those skilled in the art can easily understand other advantages and effects of this application from the content disclosed in this specification. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. This application can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of this application. It should be noted that, in the absence of conflict, the following embodiments and features in the embodiments can be combined with each other. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0021] It should be noted that the following description covers various aspects of embodiments within the scope of protection of this invention. It will be apparent that the aspects described herein can be embodied in a wide variety of forms, and any particular structure and / or function described herein is merely illustrative. Based on this application, those skilled in the art will understand that one aspect described herein can be implemented independently of any other aspect, and two or more of these aspects can be combined in various ways. For example, any number and aspects set forth herein can be used to implement the device and / or practice the method. Additionally, this device and / or method can be implemented using other structures and / or functionalities besides one or more of the aspects set forth herein.

[0022] It should also be noted that the illustrations provided in the following embodiments are only schematic representations of the basic concept of this application. The drawings only show the components related to this application and are not drawn according to the actual number, shape and size of the components in the actual implementation. In the actual implementation, the form, quantity and proportion of each component can be arbitrarily changed, and the layout of the components may also be more complex.

[0023] Furthermore, specific details are provided in the following description to facilitate a thorough understanding of the examples. However, those skilled in the art will understand that the described aspects can be practiced without these specific details.

[0024] like Figure 1 As shown in the embodiments of this application, a method for preparing basalt fiber composite material is provided, including the following steps:

[0025] Step 1: Using water or low-carbon alcohols as solvents, prepare solutions containing Bi. 3+ Solution A and cation K + 、Rb + or Cs + Furthermore, for solution B, which contains halide ions as anions, both solutions were stirred for 30–60 min. The molar concentration range of solution A was 0.0857–0.2571 mol / L, and the molar concentration range of solution B was 0.0857–0.2571 mol / L.

[0026] In one embodiment, the molar concentration ratio of solution A to solution B is 1:1 to 1:3.

[0027] Step 2: Slowly add solution B obtained in step 1 to solution A, and stir for 30-60 minutes to obtain the precursor solution.

[0028] The purpose of slowly adding solution B to solution A is to control the reaction rate, avoid local supersaturation, and improve the uniformity of the reaction.

[0029] Step 3: Place the cleaned basalt fiber in a hydrophilic surfactant solution and reflux it in a water bath at 60-80℃ for 4-8 hours to modify its hydrophilicity, thus obtaining hydrophilic basalt fiber.

[0030] Basalt fibers are cleaned with acetone solution and / or deionized water to obtain treated basalt fibers. The basalt fibers used can be commercially available, such as those produced by Zhongxian New Material Technology (Chengde) Co., Ltd.; or they can be prepared in a laboratory according to a basalt fiber raw material formula. If the basalt fiber surface is coated with a sizing agent, it needs to be degummed with acetone solution before cleaning with deionized water. If the basalt fiber surface is not coated with a sizing agent, it can be cleaned directly with deionized water.

[0031] The principle of modification is that hydrophilic surfactants possess excellent hydrophilicity. By forming a layer of hydrophilic polymer chains on the surface of basalt fibers, their hydrophilicity can be improved. This provides more active sites on the basalt fiber surface, allowing for the growth of more bismuth halides. Surfactants can be polyethylene glycol, sodium dodecyl sulfate, or dodecyltrimethylammonium bromide, etc. The hydrophilic group of the surfactant is -OH, and the concentration range of the surfactant is 30–50 g / L.

[0032] Step four: The precursor solution and hydrophilic basalt fibers are placed together in a high-pressure reactor and kept at 120-180℃ for 4-16 hours to prepare a basalt fiber composite material with bismuth halide grown on the surface.

[0033] The principle of bismuth halide growth is:

[0034] (1) Dissolution of reactants: Prepare solutions containing Bi 3+ Solution A and cation K + 、Rb + or Cs + Solution B contains halide ions as anions;

[0035] (2) Nucleation: On the surface of basalt fibers, ions aggregate under specific conditions to form the initial nuclei of bismuth halogen oxide;

[0036] (3) Depositional growth: As the reaction proceeds, more bismuth halide ions are deposited on the surface of the nucleus, forming continuous growth.

[0037] Na is present in the internal structure of basalt fibers + Ions containing a large amount of K + 、Rb + or Cs + The precursor solution of the ions was placed together in a high-pressure reactor, and under high pressure and high temperature conditions, the K+ ions were effectively promoted. + (Rb + or Cs+ ) / Na + Ion exchange is used to improve the mechanical properties of basalt fiber substrate materials.

[0038] A basalt fiber composite material with bismuth halide grown on its surface is prepared by the method described above.

[0039] The above method directly grows nano-sized bismuth halide on the surface of basalt fibers using hydrothermal or solvothermal methods. During the growth of bismuth halide, the K+ in the precursor solution... + 、Rb + or Cs + Ions and Na in basalt fibers + Ions undergo ion exchange under high temperature and high pressure, which further endows basalt fiber composite materials with higher mechanical properties, thereby expanding the application of basalt fibers in environmental remediation, composite materials and other functional properties.

[0040] In one embodiment, the treated basalt fibers are obtained by cleaning with an acetone solution and deionized water. The acetone solution can remove the wetting agent from the basalt fibers and also remove grease and dust from the surface of the basalt fibers. The acetone solution can be prepared by mixing acetone and water; in one embodiment, acetone and water can be mixed at a volume ratio of 1:1 to obtain a 50% acetone aqueous solution.

[0041] In one embodiment, solution A is prepared using Bi(NO3)3·5H2O, or BiCl3 or NaBiO3·2H2O in a solvent.

[0042] In one embodiment, solution B is prepared in a solvent using KI, KBr, KCl, RbI, RbBr, RbCl, CsI, CsBr, or CsCl.

[0043] In one embodiment, the molar ratio of solution A to solution B in step two is in the range of 1:1 to 1:3.

[0044] In one embodiment, when the high-pressure reactor is filled to 70%, the pressure inside the high-pressure reactor is not less than 0.1 MPa. Specifically, when water is used as the solvent, the pressure inside the high-pressure reactor is 0.4–1 MPa (120–180°C); when ethylene glycol is used as the solvent, the pressure inside the high-pressure reactor is 0.2–0.8 MPa (120–180°C); when ethanol is used as the solvent, the pressure inside the high-pressure reactor is 0.6–9 MPa (120–180°C); when isopropanol is used as the solvent, the pressure inside the high-pressure reactor is 1.2–18 MPa (120–180°C); and when glycerol is used as the solvent, the pressure inside the high-pressure reactor is 0.1–1.8 MPa (120–180°C).

[0045] In one embodiment, the basalt fiber composite material in step four exhibits a 5-90% increase in tensile strength and a 5-80% increase in elastic modulus compared to the basalt fiber in step three. For example, by testing the tensile strength and elastic modulus of the basalt fiber composite material using a fiber tensile strength and elongation tester, the hydrophilic basalt fiber in step three has a tensile strength range of 1600-2900 MPa and an elastic modulus range of 54-110 GPa. The basalt fiber composite material in step four has a tensile strength range of 2000-3200 MPa and an elastic modulus range of 80-130 GPa.

[0046] An application of a basalt fiber composite material with surface-grown bismuth halide is disclosed, which is used for photocatalytic degradation. In one embodiment, the basalt fiber composite material with surface-grown bismuth halide can be tested for mechanical properties and photocatalytic degradation performance. For example, the prepared basalt fiber composite material with grown bismuth halide is woven into a 3×3cm size. 2 The material, through photocatalytic degradation performance testing, can degrade 10% to 85% of Rhodamine B (10 mg / L, 50 mL) within 120 min.

[0047] Example 1

[0048] A method for preparing a basalt fiber composite material includes the following steps:

[0049] Step 1: Dissolve 9 mmol of Bi(NO3)3·5H2O in 35 mL of ethylene glycol solution, and label it solution A. Then dissolve 9 mmol of KI in 35 mL of ethylene glycol solution, and label it solution B. Stir each solution for 30 min.

[0050] Reactant dissociation:

[0051] 1. Bismuth nitrate [Bi(NO)·5H2O] dissociates into Bi 3+ and NO3 - :

[0052] Bi(NO)·5H2O→Bi 3+ +3NO - +5H2O

[0053] 2. Potassium iodide (KI) dissociates into K+. + and I - :

[0054] KI→K + +I -

[0055] Step 2: Slowly add solution B obtained in step 1 to solution A, and stir for 30 minutes to obtain the precursor solution.

[0056] Step 3: Use acetone solution and deionized water to remove the wetting agent, grease and dust from the surface of the basalt fiber to obtain cleaned basalt fiber.

[0057] Step four: The cleaned basalt fibers from step three were placed in a 50 g / L polyethylene glycol solution and refluxed in a water bath at 60°C for 4 hours to perform hydrophilic modification, resulting in hydrophilic basalt fibers. The tensile strength and elastic modulus of the hydrophilic basalt fibers were tested using a fiber tensile strength and elongation tester, yielding values ​​of 2338 MPa and 84.26 GPa, respectively. The hydrophilic basalt fibers were then woven into 3×3 cm... 2 The material, through photocatalytic degradation performance testing, showed that it could only degrade 5% of Rhodamine B (10 mg / L, 50 mL) within 120 min.

[0058] Step 5: Place the precursor solution obtained in Step 2 and the hydrophilic basalt fiber obtained in Step 4 into a 100 mL high-pressure reactor and keep it at 140 °C for 8 h to obtain a basalt fiber composite material with BiOI grown on the surface.

[0059] 1.Bi 3+ It forms bismuth iodide precipitate (BiOI) with I- and oxygen ions in the solution:

[0060] Bi 3+ +I - +O 2- →BiOI (precipitate)

[0061] 2. Ion exchange equation:

[0062] Na + 玄武岩纤维 +K + 溶液 →K + 玄武岩纤维 +Na + 溶液

[0063] Among them, O 2- The main sources are the water of crystallization of Bi(NO3)3·5H2O in the reaction system or the -OH groups in the ethylene glycol solvent.

[0064] The tensile strength and elastic modulus of the basalt fiber composite material with BiOI grown on the surface were tested using a fiber tensile strength tester, yielding values ​​of 2641 MPa and 101.85 GPa, respectively. These values ​​are higher than the 2338 MPa and 84.26 GPa obtained in step four, representing increases of 12.59% and 20.89%, respectively. The prepared composite material was then woven into a 3×3 cm diameter... 2 The material, through photocatalytic degradation performance testing, can degrade 81% of Rhodamine B (10 mg / L, 50 mL) within 120 min, which is much higher than the 5% degradation efficiency in step four.

[0065] Compare with Example 1

[0066] A method for preparing a basalt fiber composite material includes the following steps:

[0067] Step 1: Dissolve 9 mmol of Bi(NO3)3·5H2O in 35 mL of ethylene glycol solution, and label it solution A. Then dissolve 9 mmol of NaI in 35 mL of ethylene glycol solution, and label it solution B. Stir each solution for 30 min.

[0068] Step 2: Slowly add solution B obtained in step 1 to solution A, and stir for 30 minutes to obtain the precursor solution.

[0069] Step 3: Use acetone solution and deionized water to remove the wetting agent, grease and dust from the surface of the basalt fiber to obtain cleaned basalt fiber.

[0070] Step four: The cleaned basalt fibers obtained in step three were placed in a 50 g / L polyethylene glycol solution and refluxed in a water bath at 60°C for 4 hours to perform hydrophilic modification, resulting in hydrophilic basalt fibers. The tensile strength and elastic modulus of the hydrophilic basalt fibers were tested using a fiber tensile strength and elongation tester, yielding values ​​of 2338 MPa and 84.26 GPa, respectively. The hydrophilic basalt fibers were then woven into 3×3 cm... 2 The material, through photocatalytic degradation performance testing, showed that it could only degrade 5% of Rhodamine B (10 mg / L, 50 mL) within 120 min.

[0071] Step 5: The precursor solution obtained in Step 2 and the hydrophilic basalt fibers obtained in Step 4 were placed together in a 100 mL high-pressure reactor and kept at 140 °C for 8 h to obtain a basalt fiber composite material with BiOI grown on its surface. The tensile strength and elastic modulus of the basalt fiber composite material with BiOI grown on its surface were tested using a fiber tensile strength tester, and the specific values ​​were 1803 MPa and 74.98 GPa, respectively, which were lower than 2338 MPa and 84.26 GPa in Step 4, representing a decrease of 22.88% and 11.01% respectively compared to Step 4. The prepared composite material was then woven into a 3×3 cm... 2 The material, through photocatalytic degradation performance testing, can degrade 69% of Rhodamine B (10 mg / L, 50 mL) within 120 min, which is much greater than the 5% in step four and slightly less than the 81% in step five of Example 1.

[0072] Based on the experimental results of Example 1 and Comparative Example 1, this example shows a significant enhancement effect on the mechanical properties of basalt fiber substrate materials, and the prepared composite material has significant photocatalytic degradation performance.

[0073] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application.

Claims

1. A method for preparing a basalt fiber composite material with surface-grown bismuth halide, characterized in that, include: Step 1: Using water or low-carbon alcohols as solvents, prepare solutions containing Bi. 3+ Solution A and cation K + 、Rb + or Cs + The solutions B, whose anions are halide ions, are stirred for 30-60 min each; the molar concentration range of solution A is 0.0857-0.2571 mol / L, and the molar concentration range of solution B is 0.0857-0.2571 mol / L; the number of carbon atoms in the lower alcohol does not exceed 5. Step 2: Slowly add solution B obtained in step 1 to solution A, and stir for 30-60 minutes to obtain the precursor solution; The molar ratio of solution A to solution B is in the range of 1:1 to 1:3; Step 3: Place the cleaned basalt fiber in a hydrophilic surfactant solution and reflux it in a water bath at 60-80 ℃ for 4-8 h to modify it for hydrophilicity, thereby obtaining hydrophilic basalt fiber. Step four: The precursor solution and the hydrophilic basalt fiber are placed together in a high-pressure reactor and kept at 120~180 ℃ for 4~16 h to prepare a basalt fiber composite material with bismuth halide grown on the surface; the pressure inside the high-pressure reactor is not less than 0.1 MPa; The basalt fiber composite material described in step four has a tensile strength that is 5% to 90% higher and an elastic modulus that is 5% to 80% higher than that of the hydrophilic basalt fiber described in step three.

2. The preparation method according to claim 1, characterized in that, The lower alcohol mentioned in step one is any one of ethanol, ethylene glycol, isopropanol, and glycerol.

3. The preparation method according to claim 1, characterized in that, The solution A mentioned in step one is prepared using Bi(NO3)3·5H2O, BiCl3, or NaBiO3·2H2O.

4. The preparation method according to claim 1, characterized in that, The solution B mentioned in step one is prepared using KI, KBr, KCl, RbI, RbBr, RbCl, CsI, CsBr, or CsCl.

5. The preparation method according to claim 1, characterized in that, The cleaned basalt fiber is obtained by cleaning basalt fiber with acetone solution and deionized water.

6. A basalt fiber composite material with bismuth halide grown on its surface, characterized in that, The basalt fiber composite material with surface-grown bismuth halide is prepared by any one of claims 1 to 5.

7. The application of a basalt fiber composite material with surface-grown bismuth halide, characterized in that, The basalt fiber composite material with surface-grown bismuth halide as described in claim 6 is used for photocatalytic degradation.

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