Graphene heating glass fiber reinforced plastic and preparation method thereof

Abstract

The invention discloses graphene heating glass fiber reinforced plastic and a preparation method thereof. The graphene heating glass fiber reinforced plastic comprises at least one heating layer (1) and at least one heat conduction layer (2), a bonding layer (3) is arranged between the heating layer (1) and the heat conducting layer (2); and a power supply electrode (4) is arranged on at least one heating layer (1). The graphene heating glass fiber reinforced plastic overcomes thermal resistance formed by low thermal conductivity of resin and fibers, can ensure high strength, enables internal temperature of the glass fiber reinforced plastic to be rapidly conducted to the surface, improves the surface power density and heating speed of the glass fiber reinforced plastic, avoids internal overheating, and improves the heat conductivity of the glass fiber reinforced plastic. And the service life is prolonged.

Description

Technical Field

[0002] The invention relates to the technical field of composite reinforced materials, in particular to a graphene heating glass fiber reinforced plastic and a preparation method thereof. Background Art

[0003] Fiber reinforced resin (FRP) is a composite material composed of resin and fiber (such as glass fiber, ceramic fiber or basalt fiber) and other reinforcing materials. It has the characteristics of light weight, high hardness, non-conductive, high mechanical strength, corrosion resistance, etc. As one of the fiber reinforced resins (FRP), FRP can replace steel to manufacture machine parts and automobile and ship shells. For the FRP composite materials currently on the market, their excellent mechanical properties are often used.

[0004] Patent CN117468233A replaces ordinary glass fiber cloth with graphene conductive glass fiber cloth, which can generate heat after being energized, giving FRP, a traditional substrate, a new heating function in addition to mechanical insulation. However, since the conductive graphene fiber cloths are bonded by resin, and the thermal conductivity of the resin is poor, it is easy to cause the heat of the internal conductive graphene fiber cloth to be difficult to be quickly and timely discharged, which can easily cause internal overheating and affect the service life of the heating FRP, and also limit the heating power of the graphene FRP. Summary of the invention

[0005] The technical problem to be solved by the present invention is to overcome the shortcomings of the above-mentioned prior art: to provide a graphene heating fiberglass with uniform heat conduction and rapid heat conduction and a preparation method thereof.

[0006] The technical solution of the present invention is as follows: a graphene heating fiberglass, comprising at least one heating layer and at least one heat-conducting layer; an adhesive layer is provided between the heating layer and the heat-conducting layer; and a power supply electrode is provided on at least one of the heating layers.

[0007] As an optimization, the heating layer is a graphene fiber layer.

[0008] As an optimization, the material of the heat conductive layer is one or more of metal, metal oxide, metal nitride, carbon fiber, graphite, boron nitride, silicon carbide and silicon nitride.

[0009] The thermal conductive layer may be in the form of one or more of a thermal conductive foil and a thermal conductive mesh; the metal may be silver, copper, gold, aluminum, magnesium, tungsten, molybdenum, zinc, nickel, iron or the like; the metal oxide may be magnesium oxide, aluminum oxide, copper oxide, zinc oxide, zirconium oxide, titanium oxide; the metal nitride may be molybdenum nitride, iron nitride, aluminum nitride.

[0010] As an optimization, the heat-conducting layers are heat-conductingly connected, for example, through-hole heat-conducting connections between layers.

[0011] As an optimization, the material of the adhesive layer is one or more of epoxy resin, phenolic resin, polyester resin and polyimide resin.

[0012] As an optimization, the thickness of the heat conductive layer is 5 μm-1 mm.

[0013] As an optimization, at least two heat-conducting layers are included; all the heat-conducting layers are integrally formed to achieve heat-conducting connection between the multiple heat-conducting layers.

[0014] The present invention provides a method for preparing the graphene heating glass fiber reinforced plastic, comprising the following steps: 1) Lay a whole roll of thermal conductive surface material on the molding surface to form a bottom thermal conductive layer; or specifically, mix the resin and curing agent and apply them on the mold surface, and then lay a whole roll of thermal conductive surface material with the same width as the mold but in the length direction on the mold surface to form the bottom thermal conductive layer; 2) Mixing the resin and the curing agent and applying them on the upper surface of the thermal conductive surface material and then laying the graphene fiber layer; coating the two sides of the graphene fiber layer with a conductive material to form a positive and negative electrode and a power supply electrode for conductive connection; mixing the resin and the curing agent and applying them on the upper surface of the graphene fiber layer and then folding the thermal conductive surface material to bond it to the graphene fiber layer to form an upper thermal conductive layer; 3) Repeat step 2) according to the required thickness or the number of layers of the heat-conducting layer and the heating layer, so that the heat-conducting surface material is alternately folded and coated with the graphene fiber layer, and placed at room temperature for 24-48 hours to solidify and shape, and then the graphene heating fiberglass can be obtained.

[0015] The graphene fiber layer is a graphene fiber cloth. The graphene fiber cloth is a composite material formed by directly growing a graphene film on the surface of the fiber cloth, and is a commercially available product in the prior art.

[0016] The beneficial effects of the present invention are as follows: the present invention overcomes the thermal resistance formed by the low thermal conductivity of the resin and the fiber, and provides a graphene heating glass fiber reinforced plastic that can be heated and has high thermal conductivity. While ensuring high strength, the temperature inside the glass fiber reinforced plastic can be transferred to the surface faster, thereby improving the surface power density and heating speed of the glass fiber reinforced plastic, avoiding internal overheating, and improving heating stability and life. Based on the conductivity of the graphene film with nanometer thickness on the surface of the graphene fiber cloth, rapid and uniform surface heating can be achieved after power is turned on; in the graphene glass fiber reinforced plastic formed by the graphene fiber cloth and the resin, the heat generated by the heating of the graphene fiber cloth needs to be transferred layer by layer to the surface of the glass fiber reinforced plastic through the resin layer and further heats the load. Due to the low thermal conductivity of the resin, the heat transfer rate and efficiency are low, and there is a significant temperature difference between the surface and the inside of the glass fiber reinforced plastic. One solution to overcome this problem is to select a high thermal conductivity resin or to improve the thermal conductivity of the resin itself. However, the thermal conductivity of materials such as resins is difficult to improve. By doping metal particles in the resin, the thermal conductivity can be improved to a certain extent, but it may cause an electrical short circuit between the graphene fiber layers and seriously affect the mechanical strength of the glass fiber reinforced plastic. In particular, the multi-layer heat-conducting layer provided by the present invention is formed into a three-dimensional layered structure by folding a heat-conducting surface material or coiled material with the same material as the heat-conducting layer, so that the heat can not only form high thermal conductivity in the two-dimensional plane, but also form good heat conduction in the three-dimensional direction perpendicular to the layered structure, which can effectively shorten the thermal resistance of heat transfer inside the fiberglass. Research results also prove that the heat conduction rate and efficiency can be effectively improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a schematic diagram of the cross-sectional structure of the graphene heating fiberglass in Example 1.

[0018] Figure 2 This is a schematic diagram of the cross-sectional structure of the graphene heating fiberglass in Example 2.

[0019] Figure 3 This is a schematic diagram of the three-dimensional structure of the graphene heating fiberglass in Example 2.

[0020] Figure 4-6 This is a schematic diagram of the explosion structure of the graphene heating fiberglass in Example 2.

[0021] In the figure: 1. Heating layer; 2. Heat conducting layer; 3. Adhesive layer; 4. Power supply electrode. DETAILED DESCRIPTION

[0022] Embodiments of the present invention are described in detail below, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, and should not be construed as limiting the present invention.

[0023] Example 1 Figure 1 Provided is a graphene heating fiberglass, comprising four heating layers 1 and five heat-conducting layers 2; an adhesive layer 3 is provided between the heating layer 1 and the heat-conducting layer 2; and a power supply electrode 4 is provided on each heating layer 1.

[0024] The heating layer 1 is a graphene fiber layer. The material of the heat-conducting layer 2 is copper foil. The material of the adhesive layer 3 is epoxy resin. The thickness of the single-layer heat-conducting layer 2 is 0.05 mm.

[0025] The preparation method of the graphene heating glass fiber reinforced plastic comprises the following steps: 1) Spread the copper foil along the plane; 2) Mix epoxy resin and ethyleneamine in a molar ratio of 4:1 and apply it on the upper surface of the copper foil before laying the graphene fiber layer; Use conductive silver paste to coat two electrodes on both sides of the graphene fiber layer to form positive and negative ends, and use wires to lead out the power supply electrode 4; Mix epoxy resin and ethyleneamine and apply it on the upper surface of the graphene fiber layer before laying the copper foil; 3) Repeat step 2) to obtain four layers of graphene fiber layers and five layers of copper foil, and place them at room temperature for 48 hours to solidify and shape, and then you can get graphene heating fiberglass.

[0026] Example 2 The difference from Example 1 is that the copper foil of the heat-conducting layer 2 is replaced by alumina fiber cloth, and the thickness of the alumina fiber cloth is 1 mm; the epoxy resin is replaced by acetic resin, and the curing agent ethyleneamine is replaced by acetyl chloride, and two heating layers 1 and two heat-conducting layers 2 are provided.

[0027] Example 3 The difference from Example 1 is that the copper foil of the heat-conducting layer 2 is replaced by aluminum nitride fiber cloth, and the thickness of the aluminum nitride fiber cloth is 0.2 mm; the epoxy resin is replaced by spandex resin, and the curing agent ethyleneamine is replaced by polyisocyanate, and a heating layer 1 and a heat-conducting layer 2 are provided.

[0028] Example 4 The difference from Example 1 is that the copper foil of the heat-conducting layer 2 is replaced by graphite paper with a thickness of 0.2 mm, the epoxy resin is replaced by spandex resin, the curing agent vinylamine is replaced by polyisocyanate, and two heating layers 1 and two heat-conducting layers 2 are provided.

[0029] Example 5 The difference from Example 1 is that the copper foil of the heat conducting layer 2 is replaced by a copper mesh with a thickness of 0.5 mm.

[0030] Example 6 The difference from Example 1 is that the copper foil of the heat-conducting layer 2 is replaced by a composite heat-conducting layer, which is a composite of a metal heat-conducting layer and a non-metal heat-conducting layer. The composite heat-conducting layer is formed by bonding a layer of 0.1 mm thick copper foil and a layer of 0.1 mm thick graphite paper.

[0031] Example 7 Figure 2 A better graphene heating fiberglass is provided, the structure of which is as follows Figure 3-6 As shown; it includes four heating layers 1 and five heat-conducting layers 2; the five heat-conducting layers 2 are formed by folding a heat-conducting surface material with the same material as the heat-conducting layer 2 to achieve heat-conducting connection between the multiple heat-conducting layers 2; an adhesive layer 3 is provided between the heating layer 1 and the heat-conducting layer 2; and a power supply electrode 4 is provided on each heating layer 1.

[0032] The heating layer 1 is a graphene fiber layer. The heat conducting layer 2 is made of a copper mesh, and the thickness of the copper mesh is 0.1 mm. The bonding layer is made of a resin material, and the resin is an epoxy resin.

[0033] The preparation method of the graphene heating glass fiber reinforced plastic comprises the following steps: 1) Mix epoxy resin and ethyleneamine and apply them on the mold surface, and then lay a copper mesh of corresponding width but a full roll in the length direction on the mold surface; 2) Mixing epoxy resin and ethyleneamine and applying them on the surface of the copper mesh before laying the graphene fiber layer; using conductive silver paste to coat two electrodes on both sides of the graphene fiber layer to form positive and negative ends, and using copper foil to connect the electrodes to form a power supply electrode 4; mixing epoxy resin and ethyleneamine and applying them on the upper surface of the graphene fiber layer, and then folding the copper mesh to make it fit with the graphene fiber layer; 3) Repeat step 2) to obtain four layers of graphene fiber layers and five layers of copper mesh, so that the copper mesh is covered with the graphene fiber layer by alternate folding, the graphene fiber layer and the copper mesh are bonded by epoxy resin, and placed at room temperature for 48 hours to cure and shape, and after demolding, the graphene heating fiberglass can be obtained.

[0034] Comparative Example 1 The difference from Example 1 is that the heat conducting layer 2 is not provided; the glass fiber reinforced plastic sample is prepared according to the following steps: 1) Mix epoxy resin and ethyleneamine and apply them on the mold surface, and then lay a graphene fiber layer on the mold surface; 2) using conductive silver paste to coat two electrodes on both sides of the graphene fiber layer to form positive and negative ends, and using wires to lead out the power supply electrode 4; mixing epoxy resin and ethyleneamine and brushing them on the upper surface of the graphene fiber layer before laying the graphene fiber layer; 3) Repeat step 2) to obtain four graphene fiber layers, place at room temperature for 48 hours to solidify and obtain a FRP sample.

[0035] Performance Testing The power supply electrodes 4 of the graphene heating fiberglass samples prepared in Example 1 and Example 7 and the fiberglass samples prepared in Comparative Example 1 are supplied with the same voltage of 220V and current of 0.5A to ensure the same heating power. After power is applied at the same time, the thermal conductivity is judged by measuring the temperature rise of the three samples at the same time.

[0036] After one minute of power on, it was found that the temperature of the glass fiber reinforced plastic of Example 1 had reached 190°C, with a heating rate of 3.16°C / s, while the temperature of the glass fiber reinforced plastic of Comparative Example 1 was only 110°C, with a heating rate of 1.83°C / s. By adding a heat-conducting layer, the heating rate of the glass fiber reinforced plastic was increased by 73%. It was found that the temperature of the glass fiber reinforced plastic of Example 7 had reached 218°C, with a heating rate of 3.63°C / s, indicating that Example 7 has the best thermal conductivity.

[0037] The other embodiments were tested under the same test conditions: the heating rate of embodiment 2 was 2.42°C / s, that of embodiment 3 was 2.87°C / s, that of embodiment 4 was 3.95°C / s, that of embodiment 5 was 3.26°C / s, and that of embodiment 6 was 3.58°C / s.

[0038] The reason for the above differences is mainly related to the thermal conductivity of the high thermal conductivity layer itself. According to data, the thermal conductivity of various resins is 0.1~0.5 W / m·K, the thermal conductivity of copper is about 386~401W / m·K, the thermal conductivity of alumina is 30~40W / m·K, the thermal conductivity of aluminum nitride is 70~200W / m·K, and the thermal conductivity of graphite paper is 600~1000W / m·K.

[0039] The graphene heating fiberglass prepared in this embodiment is a three-dimensional layered structure, and the thermal conductive layer is folded to form a three-dimensional layered network structure, so that the heat can not only form high thermal conductivity in a two-dimensional plane, but also form good heat conduction in a three-dimensional direction perpendicular to the layered structure.

[0040] The above are only examples of the features of the present invention and do not constitute any limitation on the protection scope of the present invention. Any technical solution formed by equivalent exchange or equivalent replacement falls within the protection scope of the present invention.

Claims

1. A graphene heating glass fiber reinforced plastic, characterized in that: It comprises at least one heating layer (1) and at least one heat-conducting layer (2); an adhesive layer (3) is provided between the heating layer (1) and the heat-conducting layer (2); and a power supply electrode (4) is provided on at least one heating layer (1).

2. The graphene heating fiberglass according to claim 1, characterized in that: The heating layer (1) is a graphene fiber layer.

3. The graphene heating fiberglass according to claim 2, characterized in that: The material of the heat-conducting layer (2) is one or more of metal, metal oxide, metal nitride, carbon fiber, graphite, boron nitride, silicon carbide and silicon nitride.

4. The graphene heating fiberglass according to claim 3, characterized in that: The heat conducting layers (2) are heat conductingly connected to each other.

5. The graphene heating fiberglass according to claim 4, characterized in that: The material of the adhesive layer (3) is one or more of epoxy resin, phenolic resin, polyester resin and polyimide resin.

6. The graphene heating glass fiber reinforced plastic according to any one of claims 1 to 5, characterized in that: The thickness of the heat-conducting layer (2) is 5 μm-1 mm.

7. The graphene heating fiberglass according to claim 1 or 2, characterized in that: It comprises at least two heat-conducting layers (2); all the heat-conducting layers (2) are integrally formed to achieve heat-conducting connection between the multiple heat-conducting layers (2).

8. A method for preparing the graphene heating glass fiber reinforced plastic according to claim 7, characterized in that: The following steps are involved: 1) Laying a whole roll of heat-conducting surface material on the molding surface to form a bottom heat-conducting layer (2); 2) mixing a resin and a curing agent and applying them on the upper surface of the thermal conductive surface material, and then laying a graphene fiber layer; coating the surfaces of both sides of the graphene fiber layer with a conductive material to form positive and negative electrodes that are conductively connected to the power supply electrode (4); mixing a resin and a curing agent and applying them on the upper surface of the graphene fiber layer, and then folding the thermal conductive surface material so that it is bonded to the graphene fiber layer to form an upper thermal conductive layer (2); 3) Repeat step 2) according to the required thickness or number of layers of the heat-conducting layer (2) and the heating layer (1), so that the heat-conducting surface material is alternately folded and coated with the graphene fiber layer, and placed at room temperature for 24-48 hours to solidify and shape, thereby obtaining the graphene heating fiberglass.

9. The method for preparing graphene heating glass fiber reinforced plastic according to claim 8, characterized in that: The following steps are involved: 1) Mix the resin and curing agent and apply them on the mold surface, and then lay a thermal conductive surface material with the same width as the mold but in a full roll in the length direction on the mold surface to form a thermal conductive layer (2); 2) mixing a resin and a curing agent and applying the mixture to the other surface of the heat conductive layer (2) and then laying a graphene fiber layer; coating the surfaces of both sides of the graphene fiber layer with a conductive material to form positive and negative electrodes that are electrically connected to the power supply electrode (4); mixing a resin and a curing agent and applying the mixture to the upper surface of the graphene fiber layer and then folding the heat conductive surface material so that it is bonded to the graphene fiber layer to form an upper heat conductive layer (2); 3) Repeat step 2) according to the required thickness or number of layers of the heat-conducting layer (2) and the heating layer (1), so that the heat-conducting surface material is alternately folded and coated with the graphene fiber layer, and placed at room temperature for 24-48 hours to solidify and shape, and after demolding, the graphene heating fiberglass can be obtained.

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