A method for preparing a graphene-coated conductive glass fiber mesh

Abstract

The application discloses a preparation method of graphene-coated conductive glass fiber mesh cloth, which is composed of the following specific steps: (1) glass fiber mesh cloth is soaked in a silane coupling agent aqueous solution to perform surface silanization modification on the surface of the glass fiber, and then repeated drying and water washing are performed to obtain silane coupling agent modified glass fiber mesh cloth; (2) a proper amount of graphene powder is added into a polyethylene imine aqueous solution, and then dispersion treatment is performed to obtain a graphene dispersion liquid; and (3) the silane coupling agent modified glass fiber mesh cloth obtained in the step (1) is soaked in the graphene dispersion liquid obtained in the step (2), and finally drying is performed to obtain the graphene-coated conductive glass fiber mesh cloth. The prepared conductive glass fiber mesh cloth not only has adjustable conductivity, but also can widen the application of the glass fiber mesh cloth and a composite material thereof; and the whole preparation process is simple and efficient, low in cost and easy to realize large-scale production.

Description

Technical Field

[0001] This invention relates to conductive glass fiber mesh fabric, and more specifically to a method for preparing conductive glass fiber mesh fabric. Background Technology

[0002] Fiberglass mesh is a commonly used material in construction, possessing superior mechanical properties such as corrosion resistance, light weight, and high strength. It is frequently used to prepare widely applicable fiberglass mesh-reinforced concrete / mortar and fiberglass mesh-reinforced composite plastics with excellent mechanical properties. However, the inherent electrical insulation properties of fiberglass mesh limit its application in the field of functional composite materials.

[0003] Graphene is a two-dimensional carbon material with a honeycomb crystalline structure and excellent antibacterial, electrothermal, electrical, and sensing properties. It is currently widely used in polymer composites, thermal conductivity, electromagnetic shielding, and micro / nano sensing. Effectively combining graphene with glass fiber mesh could impart the superior properties of graphene to the glass fiber mesh, expanding its applications in functional composite materials. Graphene-coated glass fiber mesh holds promise for applications in concrete load monitoring, smart manhole covers, electrically heated concrete, and water treatment.

[0004] However, due to the inherent properties of graphene, existing methods for preparing glass fiber mesh cannot effectively and stably fuse graphene with glass fiber mesh. The stability of the bond between the glass fiber mesh and graphene in the prepared composite glass fiber mesh is not high, which will greatly affect the performance of the prepared composite glass fiber mesh in terms of conductivity, heating, etc. Summary of the Invention

[0005] To address the shortcomings of existing glass fiber mesh fabrics in terms of functionality, this invention proposes a method for preparing graphene-coated conductive glass fiber mesh fabric. This method can achieve a stable combination of graphene and glass fiber mesh fabric, forming a conductive glass fiber mesh fabric with stable performance.

[0006] To achieve the above objectives, the method for preparing graphene-coated conductive glass fiber mesh provided by the present invention comprises the following specific steps:

[0007] (1) The glass fiber mesh was soaked in an aqueous solution of silane coupling agent to modify the surface of the glass fiber by surface silanization, and then repeatedly dried and washed to obtain the silane coupling agent modified glass fiber mesh.

[0008] (2) Add an appropriate amount of graphene powder to a polyethyleneimine aqueous solution and then disperse it to obtain a graphene dispersion.

[0009] (3) The silane coupling agent modified glass fiber mesh obtained in step (1) is immersed in the graphene dispersion obtained in step (2), and finally dried to obtain graphene-coated conductive glass fiber mesh.

[0010] In some examples of the present invention, the silane coupling agent in step (1) includes, but is not limited to, one or more of the following: epoxy alkyl silane coupling agent, 3,4-epoxycyclohexane silane coupling agent, and γ-(2,3-epoxypropane) hydrocarbon silane coupling agent.

[0011] In some examples of the present invention, the concentration of the aqueous solution of the silane coupling agent in step (1) is 0.2 to 30 wt%.

[0012] In some examples of the present invention, the soaking time in steps (1) and (3) is 0.05 to 5 hours.

[0013] In some examples of the present invention, the concentration of the polyethyleneimine aqueous solution in step (2) is 2-50 wt%.

[0014] In some embodiments of the present invention, the graphene comprises, but is not limited to, one or more of 1 to 5 single-atom layers.

[0015] In some examples of the present invention, the concentration of the graphene dispersion formed in step (2) is 1 to 200 mg / mL, and the mass ratio of graphene to polyethyleneimine is 1:5 to 5:1.

[0016] In some embodiments of the present invention, the dispersion process in step (2) takes 0.5 to 24 hours.

[0017] The beneficial effects of this invention are reflected in:

[0018] (1) The present invention utilizes the reactivity between epoxy silane coupling agent and amino group to achieve stable coating of graphene onto glass fiber mesh, which has excellent water resistance and durability.

[0019] (2) The graphene-coated conductive glass fiber mesh obtained by the present invention has adjustable conductivity, which can meet the application requirements of sensing, electric heating, photothermal, water treatment and other fields, and broaden the application of glass fiber mesh and its composite materials.

[0020] (3) When implementing the present invention, the whole process is simple, efficient and low-cost, and the amount of organic solvent used is small, which is conducive to its large-scale application.

[0021] (4) The present invention does not damage the original mechanical properties of the glass fiber mesh, and the surface affinity can be improved after surface silanization treatment and graphene coating, making it easier to combine with polymers, concrete and other materials during use.

[0022] Other features and advantages of the present invention will be described in the following detailed description section. Detailed Implementation

[0023] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further explained below with reference to specific examples.

[0024] Addressing the issue that glass fiber mesh and graphene cannot be effectively and stably combined due to their respective properties, the inventors discovered through extensive creative work that by simultaneously modifying both glass fiber mesh and graphene, they can be organically combined to form a stable and reliable composite structure.

[0025] Building on this foundation, the inventors further discovered through extensive creative work that glass fiber mesh and graphene can be modified using epoxy silane coupling agents and polyethyleneimine.

[0026] Furthermore, the present invention creatively uses epoxy-based silane coupling agents and polyethyleneimine to modify the surfaces of glass fiber mesh and graphene, respectively, and then utilizes the reactivity between epoxy groups and imino groups to prepare a graphene-stable coated conductive glass fiber mesh.

[0027] In the resulting conductive glass fiber mesh, graphene is reliably and stably coated onto the glass fiber mesh based on the reactive interaction between epoxy and imino groups. This graphene coating endows the glass fiber mesh with properties not originally present in the glass fiber mesh, such as antibacterial, electrothermal, conductive, and sensing properties. Therefore, based on these properties, this conductive glass fiber mesh can be effectively applied in fields such as concrete load monitoring, smart manhole covers, electrically heated concrete, water treatment, and smart plastic pipes.

[0028] The present invention further provides a method for preparing graphene-coated conductive glass fiber mesh, thereby preparing a conductive glass fiber mesh with stable and reliable performance.

[0029] The preparation method here consists of the following three steps, and the whole process is simple and efficient:

[0030] (1) The glass fiber mesh was soaked in an aqueous solution of silane coupling agent to modify the surface of the glass fiber by surface silanization, and then repeatedly dried and washed to obtain the silane coupling agent modified glass fiber mesh.

[0031] (2) A certain amount of graphene powder is added to a polyethyleneimine aqueous solution, and then a graphene dispersion is obtained by mechanical dispersion treatment. At the same time, the polyethyleneimine will simultaneously and effectively modify the surface of the graphene.

[0032] (3) The silane coupling agent modified glass fiber mesh obtained in step (1) is immersed in the graphene dispersion obtained in step (2). During this process, the surface-modified graphene reacts with the epoxy groups on the surface-modified glass fiber in the glass fiber mesh based on the imino groups on it to achieve a stable connection structure. Therefore, the graphene is uniformly and stably coated on the glass fiber. Finally, the graphene-coated conductive glass fiber mesh is obtained by drying.

[0033] In some embodiments of the present invention, in order to effectively modify the surface of the glass fibers in the glass fiber mesh, the silane coupling agent used in step (1) is preferably one or more of the following: epoxy alkyl silane coupling agent, 3,4-epoxycyclohexane silane coupling agent, and γ-(2,3-epoxypropane) hydrocarbon silane coupling agent.

[0034] Based on this silane coupling agent, the surface of glass fibers in glass fiber mesh can be efficiently modified without damaging the original mechanical properties of the glass fiber mesh.

[0035] For example, the silane coupling agent here can be 3-glycidyl etheroxypropyltrimethoxysilane (KH560), trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane (A-186), 3-glycidyl etheroxypropylmethyldiethoxysilane (KH563), etc.

[0036] In some embodiments of the present invention, when forming an aqueous solution of silane coupling agent based on the specific silane coupling agent described above in step (1), the concentration of the aqueous solution of silane coupling agent is 0.2–30 wt%. The present invention has determined through numerous experiments that, based on the specific components described above, only an aqueous solution of silane coupling agent of such concentration can effectively modify the surface of the glass fibers in the glass fiber mesh without damaging the original mechanical properties of the glass fiber mesh.

[0037] If the concentration is too low, the modification effect will be unsatisfactory; if the concentration is too high, it will affect the original mechanical properties of the glass fiber mesh.

[0038] For example, the concentration of the silane coupling agent aqueous solution can be 0.2wt%, 0.5wt%, 1.0wt%, 1.5wt%, 1.8wt%, 2.2wt%, 2.8wt%, 3wt%, 3.8wt%, 4.1wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, or 30wt%.

[0039] In some embodiments of the present invention, in step (1) of the present invention, when the glass fiber mesh is soaked in the aqueous solution of the silane coupling agent of the above-mentioned components and concentrations for surface silanization modification treatment, the soaking time is 0.05 to 5 hours to ensure the surface silanization modification treatment effect, and to avoid the effect of too short a treatment time being unaffected, while too long a treatment time affecting the original mechanical properties of the glass fiber mesh.

[0040] For example, the soaking time can be 0.05h, 0.1h, 0.12h, 0.18h, 0.2h, 0.3h, 0.8h, 1h, 1.5h, 1.8h, 2h, 2.4h, 2.7h, 3h, 3.4h, 3.8h, 4h, 4.3h, 4.7h, 4.9h, 5h, etc.

[0041] In some embodiments of the present invention, the graphene used in step (2) of the present invention specifically employs one or more of 1 to 5 single-atom layers.

[0042] Correspondingly, the concentration of the polyethyleneimine aqueous solution formed in step (2) of the present invention is 2-50 wt%. The present invention has determined through a large number of experiments that only by using a polyethyleneimine aqueous solution of such concentration on the basis of the above-mentioned graphene can the graphene surface be effectively modified so as to combine with the glass fibers in the glass fiber mesh cloth that has been surface modified in step (1).

[0043] For example, the concentration of the polyethyleneimine aqueous solution can be 2wt%, 2.2wt%, 2.8wt%, 3wt%, 3.8wt%, 4.1wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%. wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 3 7wt%, 38wt%, 39wt%, 40wt%, 41wt%, 42wt%, 43wt%, 44wt%, 45wt%, 46wt%, 47wt%, 48wt%, 49wt%, 50wt%.

[0044] In some embodiments of the present invention, step (2) of the present invention is based on the graphene with the above-mentioned specific structure and the polyethyleneimine aqueous solution of a specific concentration. When adding graphene powder, the concentration of the graphene dispersion is 1 to 200 mg / mL, and the mass ratio of graphene to polyethyleneimine is 1:5 to 5:1, thereby further promoting and improving the effect of modifying the graphene surface.

[0045] For example, the concentration of the graphene dispersion formed here can be 1 mg / mL, 2 mg / mL, 5 mg / mL, 10 mg / mL, 14 mg / mL, 20 mg / mL, 25 mg / mL, 30 mg / mL, 33 mg / mL, 38 mg / mL, 40 mg / mL, 46 mg / mL, 50 mg / mL, 58 mg / mL, 60 mg / mL, 65 mg / mL, 70 mg / mL, 76 mg / mL, 80 mg / mL, 82 mg / mL, 86 mg / mL, 90 mg / mL, 95 mg / mL, 98 mg / mL, or 100 mg / mL. L, 110mg / mL, 120mg / mL, 125mg / mL, 130mg / mL, 137mg / mL, 140mg / mL, 144mg / mL, 148mg / mL, 150mg / mL, 152mg / mL, 158mg / mL, 160mg / mL , 164mg / mL, 169mg / mL, 170mg / mL, 171mg / mL, 176mg / mL, 180mg / mL, 183mg / mL, 186mg / mL, 190mg / mL, 193mg / mL, 197mg / mL, 200mg / mL, etc.

[0046] The mass ratio of graphene to polyethyleneimine can be 1:5, 2:5, 3:5, 4:5, 1:1, 1.5:1, 2:1, 2.3:1, 2.5:1, 2.8:1, 3:1, 3.4:1, 3.6:1, 4:1, 4.3:1, 4.6:1, 4.8:1, 5:1, etc.

[0047] In some embodiments of the present invention, when dispersing the added graphene powder in step (2), the mechanical treatment includes, but is not limited to, stirring, ultrasonication, and grinding, for a time of 0.5 to 24 hours, thereby enabling the added graphene powder to be fully and uniformly dispersed in the polyethyleneimine aqueous solution.

[0048] In some embodiments of the present invention, when the silane coupling agent modified glass fiber mesh obtained in step (1) is immersed in the graphene dispersion obtained in step (2) for reaction treatment in step (3), the immersion time is 0.05 to 5 hours to ensure the surface silanization modification effect, and to avoid the effect of too short a treatment time, which is not affected, and too long a treatment time, which affects the original mechanical properties of the glass fiber mesh.

[0049] For example, the soaking time can be 0.05h, 0.1h, 0.12h, 0.18h, 0.2h, 0.3h, 0.8h, 1h, 1.5h, 1.8h, 2h, 2.4h, 2.7h, 3h, 3.4h, 3.8h, 4h, 4.3h, 4.7h, 4.9h, 5h, etc.

[0050] The present invention can form a conductive glass fiber mesh by organically combining the above three steps. The whole process is simple, efficient, and low-cost, with a small amount of organic solvent used, which is conducive to its large-scale application. At the same time, the stable coating of the glass fiber mesh by graphene in the formed conductive glass fiber mesh gives the conductive glass fiber mesh adjustable conductivity, which can meet the application requirements of sensing, electric heating, photothermal, water treatment and other fields, thus broadening the application of glass fiber mesh and its composite materials.

[0051] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments that do not specify specific conditions are generally determined according to national standards. If no corresponding national standard exists, then generally accepted international standards, conventional conditions, or conditions recommended by the manufacturer are followed.

[0052] Unless otherwise defined or stated, all technical and scientific terms used herein have the same meaning as are familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be used in the methods of this invention.

[0053] Example 1

[0054] In this example, 3-glycidyl etheroxypropyltrimethoxysilane (KH560) is used to form an aqueous solution of silane coupling agent to perform surface silanization modification on the glass fiber surface in the glass fiber mesh.

[0055] Therefore, the process for preparing the graphene-coated conductive glass fiber mesh in this example is as follows:

[0056] First, 3-glycidyl etheroxypropyltrimethoxysilane (KH560) was dissolved in a water / methanol / acetic acid mixture with a pH of 4-5 to obtain an aqueous solution of KH560 with a concentration of 5 wt%.

[0057] Next, the glass fiber mesh was immersed in KH560 aqueous solution to modify the surface of the glass fiber by surface silanization. Then, the residual methanol and acetic acid were removed by repeated drying and washing to obtain KH560 modified glass fiber mesh.

[0058] Next, 20g of graphene powder was added to 100g of polyethyleneimine aqueous solution with a concentration of 20wt%, and then the mixture was ground for 5h to obtain a graphene dispersion with polyethyleneimine assistance.

[0059] Finally, the KH560 modified glass fiber mesh was immersed in the obtained graphene dispersion for 2 hours, and then dried to obtain graphene-coated conductive glass fiber mesh.

[0060] The conductive glass fiber mesh fabric prepared in this example was characterized, and the results showed that its conductivity was 3230 S / m, and its conductivity did not decrease significantly after 10 cycles of immersion and drying.

[0061] The characterization methods and requirements described here are general in this field and will not be elaborated upon here.

[0062] Example 2

[0063] In this example, trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane (A-186) is used to form an aqueous solution of silane coupling agent to modify the surface of glass fibers in the glass fiber mesh.

[0064] Therefore, the process for preparing the graphene-coated conductive glass fiber mesh in this example is as follows:

[0065] First, trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane (A-186) was dissolved in a water / methanol / acetic acid mixture with a pH of 4-5 to obtain an aqueous solution of A-186 with a concentration of 2 wt%.

[0066] Next, the glass fiber mesh was immersed in an A-186 aqueous solution to modify the surface of the glass fiber by surface silanization. Then, the residual methanol and acetic acid were removed by repeated drying and washing to obtain the A-186 modified glass fiber mesh.

[0067] Next, 4g of graphene powder was added to 100g of a 10wt% aqueous solution of polyethyleneimine, and then the mixture was ultrasonically treated for 1 hour to obtain a graphene dispersion with polyethyleneimine assistance. The resulting A-186 modified glass fiber mesh was then immersed in the graphene dispersion for 2 hours and finally dried to obtain a graphene-coated conductive glass fiber mesh.

[0068] The conductive glass fiber mesh fabric prepared in this example was characterized, and the results showed that its conductivity was 850 S / m.

[0069] The characterization methods and requirements described here are general in this field and will not be elaborated upon here.

[0070] Example 3

[0071] In this example, 3-glycidyl etheroxypropylmethyldiethoxysilane (KH563) is used to form an aqueous solution of silane coupling agent to perform surface silanization modification on the surface of glass fibers in the glass fiber mesh.

[0072] Therefore, the process for preparing the graphene-coated conductive glass fiber mesh in this example is as follows:

[0073] First, 3-glycidyl etheroxypropylmethyldiethoxysilane (KH563) was dissolved in a water / methanol / acetic acid mixture with a pH of 4-5 to obtain an aqueous solution of KH563 with a concentration of 5 wt%.

[0074] Next, the glass fiber mesh was immersed in KH563 aqueous solution to modify the surface of the glass fiber by surface silanization. Then, the residual methanol and acetic acid were removed by repeated drying and washing to obtain KH563 modified glass fiber mesh.

[0075] Next, 0.5 g of graphene powder was added to 100 g of polyethyleneimine aqueous solution with a concentration of 10 wt%, and then the mixture was stirred for 2 h to obtain a graphene dispersion with polyethyleneimine assistance.

[0076] Finally, the KH563 modified glass fiber mesh was immersed in the obtained graphene dispersion for 2 hours, and then dried to obtain graphene-coated conductive glass fiber mesh.

[0077] The conductive glass fiber mesh fabric prepared in this example was characterized, and the results showed that its conductivity was 0.8 S / m. Through tensile testing, its conductivity decreased with the increase of elongation at break.

[0078] The characterization methods and requirements described here are general in this field and will not be elaborated upon here.

[0079] As can be seen from the above examples, the graphene-coated conductive glass fiber mesh obtained based on the present invention has adjustable conductivity, which can meet the application requirements in fields such as sensing, electric heating, photothermal, and water treatment, thus broadening the application of glass fiber mesh and its composite materials.

[0080] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing graphene-coated conductive glass fiber mesh, characterized in that, The preparation method consists of the following specific steps: (1) The glass fiber mesh was soaked in an aqueous solution of epoxy silane coupling agent to modify the surface of the glass fiber by surface silanization, and then repeatedly dried and washed to obtain silane coupling agent modified glass fiber mesh. (2) Add an appropriate amount of graphene powder to a polyethyleneimine aqueous solution and then perform dispersion treatment to obtain a graphene dispersion. (3) The silane coupling agent modified glass fiber mesh obtained in step (1) is immersed in the graphene dispersion obtained in step (2), and finally dried to obtain graphene-coated conductive glass fiber mesh.

2. The method for preparing graphene-coated conductive glass fiber mesh according to claim 1, characterized in that, The silane coupling agent in step (1) includes, but is not limited to, one or more of epoxy alkyl silane coupling agents and 3,4-epoxycyclohexane silane coupling agents.

3. The method for preparing graphene-coated conductive glass fiber mesh according to claim 2, characterized in that, The concentration of the silane coupling agent aqueous solution in step (1) is 0.2~30 wt%.

4. The method for preparing graphene-coated conductive glass fiber mesh according to claim 1, characterized in that, The soaking time described in steps (1) and (3) is 0.05~5h.

5. The method for preparing graphene-coated conductive glass fiber mesh according to claim 1, characterized in that, The concentration of the polyethyleneimine aqueous solution in step (2) is 2~50 wt%.

6. The method for preparing graphene-coated conductive glass fiber mesh according to claim 1, characterized in that, The graphene comprises, but is not limited to, one or more of 1 to 5 single-atom layers.

7. The method for preparing graphene-coated conductive glass fiber mesh according to claim 1, characterized in that, The concentration of the graphene dispersion formed in step (2) is 1~200 mg / mL, and the mass ratio of graphene to polyethyleneimine is 1:5~5:

1.

8. The method for preparing graphene-coated conductive glass fiber mesh according to claim 1, characterized in that, The dispersion process in step (2) takes 0.5 to 24 hours.