Carbon fiber / metal fiber composite reinforcing material and method for manufacturing the same

Abstract

The application discloses a carbon fiber / metal fiber composite reinforcing material and a preparation method thereof. The carbon fiber / metal fiber composite reinforcing material comprises: a carbon fiber tows, an outer surface of the carbon fiber tows is covered with a reinforcing fiber layer, an outer surface of the reinforcing fiber layer is covered with a second epoxy resin coating layer, the reinforcing fiber layer is formed by winding inner layer composite filaments on the surface of the carbon fiber tows, and the inner layer composite filaments comprise: aluminum-magnesium alloy monofilaments and a first epoxy resin coating layer covering the outer surface of the aluminum-magnesium alloy monofilaments. The multilayer structure laminated plate prepared from the carbon fiber / metal fiber composite reinforcing material has certain improvement in tensile strength, bending strength, interlaminar shear strength, thermal expansion coefficient, temperature resistance range and impact toughness compared with a traditional carbon fiber plate.

Description

Technical Field

[0001] This invention belongs to the field of composite material technology, specifically relating to a carbon fiber / metal fiber composite reinforced material and its preparation method. Background Technology

[0002] Traditional carbon fiber reinforced composites (such as carbon fiber cloth or prepreg laminates) are widely used due to their high specific strength, high specific modulus, and lightweight properties. However, these materials still have some significant drawbacks: 1. Limited stress-bearing capacity and damage tolerance: They are prone to brittle fracture, delamination, or cracking under large impact loads or complex stress states, exhibiting insufficient toughness. 2. Weak interlaminar properties: The interlaminar shear strength (ILSS) is typically low, making carbon fiber reinforced composites susceptible to damage. 3. Insufficient thermal stability: The coefficient of thermal expansion (CTE) of carbon fibers differs significantly from that of commonly used resin matrices, easily generating interfacial thermal stress under alternating temperature environments, leading to performance degradation or even debonding failure, thus limiting the operating temperature range. 4. When connecting with other components (especially metal components), the difference in CTE may cause stress concentration at the connection points between the carbon fiber reinforced composite and other components.

[0003] To overcome the aforementioned shortcomings, existing technologies have attempted various modification methods (such as adding nanofillers, interlaminar toughening, and blending with other fibers), but the effects are limited or the processes are complex. Therefore, developing a novel carbon fiber composite material that can significantly improve interlaminar properties, toughness, and thermal stability while maintaining high strength has significant application value. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a carbon fiber / metal fiber composite reinforcement material.

[0005] Another object of the present invention is to provide a method for preparing the above-mentioned carbon fiber / metal fiber composite reinforced material.

[0006] Another object of the present invention is to provide a method for preparing a multilayer laminate.

[0007] Another objective of this invention is to provide a multilayer laminate obtained by the above method, which is suitable for fields with stringent requirements for the comprehensive performance of materials, such as aerospace structural components, lightweight automotive parts, and high-end sports equipment.

[0008] The objective of this invention is achieved through the following technical solution.

[0009] A carbon fiber / metal fiber composite reinforcement material includes: a carbon fiber bundle, a reinforcing fiber layer covering the outer surface of the carbon fiber bundle, and a second epoxy resin coating layer covering the outer surface of the reinforcing fiber layer. The reinforcing fiber layer is formed by an inner composite filament wound around the surface of the carbon fiber bundle. The inner composite filament includes: an aluminum-magnesium alloy monofilament and a first epoxy resin coating layer covering the outer surface of the aluminum-magnesium alloy monofilament.

[0010] In the above technical solution, the thickness of the second epoxy resin coating layer is 50-100 μm, and the second epoxy resin coating layer contains nanoparticles (to enhance wear resistance). The particle size of the nanoparticles is 50-100 nm, and the nanoparticles are nano SiO2.

[0011] In the above technical solution, the diameter of the aluminum-magnesium alloy monofilament is 0.1-0.3 mm, the thickness of the first epoxy resin coating layer is 5-15 μm, and the first epoxy resin coating layer includes epoxy resin.

[0012] In the above technical solution, the diameter of the carbon fiber bundle is 1 to 200 μm.

[0013] In the above technical solution, the inner composite filament is wound in a periodic S-shaped or serpentine waveform on the carbon fiber bundle, wherein the winding angle is 30° to 60° (the winding direction of the inner composite filament is 30° to 60° with the carbon fiber bundle), and the difference in winding angle between two adjacent inner composite filaments is ≥15°.

[0014] In the above technical solution, an oxide film with a thickness of 1 to 3 μm is formed on the outer surface of the aluminum-magnesium alloy monofilament, and the oxide film is formed by anodic oxidation.

[0015] In the above technical solution, aluminum-magnesium alloy rods are subjected to multiple cold drawing processes, with a single deformation amount of 15% to 20%, to obtain single wires. The single wires are then anodized to obtain aluminum-magnesium alloy single wires.

[0016] In the above technical solution, the diameter of the aluminum-magnesium alloy rod is 10-15 mm, and the magnesium content in the aluminum-magnesium alloy rod is 2-8 wt%.

[0017] In the above technical solution, sulfuric acid is used as the electrolyte for the anodic oxidation process.

[0018] In the above technical solution, the method for obtaining the inner layer composite wire includes: coating the outer surface (circumferential surface) of the aluminum-magnesium alloy monofilament with a first epoxy resin mixture, pre-curing it, and forming a first epoxy resin coating layer on the outer surface of the aluminum-magnesium alloy monofilament to obtain the inner layer composite wire.

[0019] Specifically, the method for obtaining the inner composite filament includes: coating an aluminum-magnesium alloy monofilament by passing it through a tank containing a first epoxy resin mixture at a speed of 5-10 m / min. The temperature of the first epoxy resin mixture in the tank is 30-40°C, the epoxy value of the epoxy resin in the first epoxy resin mixture is 0.4-0.54 eq / 100g, and the viscosity of the first epoxy resin mixture is 500-800 mPa·s.

[0020] In the above technical solution, the pre-curing temperature is 60-90℃ and the pre-curing time is 20-60min.

[0021] In the above technical solution, the coating is applied by dip coating.

[0022] The preparation method of the above-mentioned carbon fiber / metal fiber composite reinforced material includes the following steps:

[0023] Step 1: Wind 1 to 10 layers of the inner composite filaments onto the surface of the carbon fiber bundle to obtain a reinforcing fiber layer on the surface of the carbon fiber bundle;

[0024] In step 1, the carbon fiber tow is T300-12k, T300-24k, or T700-24k.

[0025] In step 1, the winding is performed on a CNC winding machine at a speed of 20-80 r / min.

[0026] Step 2: Coat the surface of the reinforcing fiber layer with epoxy resin containing nanoparticles, and cure in stages to form a second epoxy resin coating layer on the surface of the reinforcing fiber layer, thereby obtaining a carbon fiber / metal fiber composite reinforcing material.

[0027] In step 2, the step curing includes: curing at 120-130℃ for 1-3 hours at 0.5-1 MPa, followed by curing at 130-160℃ for 3-5 hours.

[0028] In step 2, the coating is applied by roller coating or spraying.

[0029] In step 2, the content of nanoparticles in the epoxy resin containing nanoparticles is 5-10 wt%.

[0030] A method for preparing a multilayer laminate includes: 5 to 50 composite layers arranged in layers, with an epoxy resin bonding layer connecting adjacent composite layers, and each composite layer being composed of multiple parallel carbon fiber / metal fiber composite reinforcing materials arranged closely together.

[0031] In the above technical solution, the thickness of the multilayer laminate is 2 to 20 mm.

[0032] In the above technical solution, the thickness of each epoxy resin adhesive layer is 10-20 μm.

[0033] A method for preparing a multilayer structural laminate includes: stacking multiple carbon fiber / metal fiber composite reinforcing materials into a multilayer composite layer to obtain a multilayer structural laminate, wherein, during the stacking process, a second epoxy resin mixture is coated between adjacent composite layers, and after curing, an epoxy resin bonding layer is formed between adjacent composite layers, wherein the second epoxy resin mixture includes epoxy resin.

[0034] In the method for preparing multilayer laminates, the curing temperature is 130–160℃ and the pressure is 2–5 MPa.

[0035] In the above technical solution, the temperature of the second epoxy resin mixture is 30-40℃, the epoxy value of the epoxy resin in the second epoxy resin mixture is 0.4-0.54eq / 100g, and the viscosity of the second epoxy resin mixture is 500-800mPa·s.

[0036] In the above technical solution, the density of the multilayer laminate is 1.8–2.2 g / cm³. 3 .

[0037] The above-mentioned multi-layered laminated panels are used in aerospace structural components, lightweight automotive parts, and / or high-end sports equipment.

[0038] The tensile strength, flexural strength, interlaminar shear strength, coefficient of thermal expansion, temperature range, and impact toughness of the aforementioned multi-layered laminate are far superior to those of traditional carbon fiber sheets (such as those purchased from Toho Carbon Fiber, model UM55). The test results are as follows.

[0039]

[0040]

[0041] Through the aforementioned special structural design (S-shaped / serpentine arrangement) and material combination / process, the multilayer laminate prepared from the carbon fiber / metal fiber composite reinforcement material of this invention achieves significant technical advantages compared to traditional carbon fiber plates (CFRP):

[0042] (1) Excellent interlaminar properties: The S-shaped / serpentine movement of the inner composite yarn effectively "rivets" the interlaminar layers, greatly improving the interlaminar shear strength (ILSS) and significantly suppressing delamination;

[0043] (2) High toughness and damage tolerance: The introduction of reinforcing fiber layers and special structural design significantly improve the material’s impact resistance and fracture toughness;

[0044] (3) Excellent thermal stability: The addition of the reinforcing fiber layer reduces the overall coefficient of thermal expansion (CTE) of the composite material, making it closer to commonly used structural materials (such as aluminum alloys), reducing thermal stress, and at the same time broadening the effective operating temperature range of the material (-50℃~200℃).

[0045] (4) High strength and lightweight: After the introduction of the reinforcing metal fiber layer, it still maintains tensile and bending strengths that are much higher than those of traditional carbon fiber plates (CFRP), but without significantly increasing the density. Attached Figure Description

[0046] Figure 1 This is a schematic diagram of a carbon fiber / metal fiber composite reinforced material. Detailed Implementation

[0047] The technical solution of the present invention will be further described below with reference to specific embodiments.

[0048] In the following embodiments, carbon fiber / metal fiber composite reinforcement materials are as follows: Figure 1 As shown, it includes: carbon fiber bundles, a reinforcing fiber layer covering the outer surface of the carbon fiber bundles, and a second epoxy resin coating layer covering the outer surface of the reinforcing fiber layer. The reinforcing fiber layer is formed by inner composite filaments wound around the surface of the carbon fiber bundles. The inner composite filaments include: aluminum-magnesium alloy monofilaments and a first epoxy resin coating layer covering the outer surface of the aluminum-magnesium alloy monofilaments.

[0049] Example 1

[0050] A method for preparing a multilayer laminate includes: stacking multiple carbon fiber / metal fiber composite reinforcement materials into 6 composite layers (each composite layer is composed of multiple parallel carbon fiber / metal fiber composite reinforcement materials arranged closely together), to obtain a multilayer laminate with a thickness of approximately 3 mm (density of 2.1 g / cm³). 3 In this process, during the stacking process, a second epoxy resin mixture is coated (immersed) between adjacent composite layers. After curing (curing temperature 150℃, pressure 3MPa, curing time 300min), an epoxy resin adhesive layer with a thickness of 15μm is formed between adjacent composite layers. The second epoxy resin mixture is a mixture of bisphenol A type epoxy resin (E-51) and diethylenetriamine. The concentration of diethylenetriamine in the second epoxy resin mixture is 12wt%, the temperature of the second epoxy resin mixture is 35℃, the epoxy value of the epoxy resin (E-51) in the second epoxy resin mixture is 0.51eq / 100g, and the viscosity of the second epoxy resin mixture is 650mPa·s.

[0051] The preparation method of the above-mentioned carbon fiber / metal fiber composite reinforced material includes the following steps:

[0052] Step 1: On a CNC winding machine, one layer of inner composite filament is wound onto the surface of the carbon fiber bundle to obtain a reinforcing fiber layer. During the winding process, the inner composite filament is wound on the carbon fiber bundle in a periodic S-shaped waveform. The winding angle is 45° (the winding direction of the inner composite filament is at 45° to the carbon fiber bundle), the winding speed is 30 r / min, the carbon fiber bundle is T300-12k, and the diameter of the carbon fiber bundle is 52 μm.

[0053] The method for obtaining the inner composite filament includes: coating the outer surface of an aluminum-magnesium alloy monofilament with a first epoxy resin mixture by dip coating, specifically including: passing the aluminum-magnesium alloy monofilament through a tank containing the first epoxy resin mixture at a speed of 8 m / min, and then pre-curing it at 80℃ for 30 min to form a first epoxy resin coating layer with a thickness of 10 μm on the outer surface of the aluminum-magnesium alloy monofilament, thereby obtaining an inner composite filament with a diameter of 0.224 mm. The first epoxy resin mixture is a mixture of bisphenol A type epoxy resin (E-51) and diethylenetriamine, the concentration of diethylenetriamine in the first epoxy resin mixture is 12 wt%, the temperature of the first epoxy resin mixture in the tank is 35℃, the epoxy value of the epoxy resin (E-51) in the first epoxy resin mixture is 0.51 eq / 100 g, and the viscosity of the first epoxy resin mixture is 650 mPa·s.

[0054] The method for obtaining aluminum-magnesium alloy monofilaments includes: cold drawing 10 times with an aluminum-magnesium alloy rod (grade 5A06, magnesium content 6wt%) with a diameter of 12mm, wherein the deformation per pass of the first 9 passes is 20%, and then the 10th pass is cold drawn (deformation per pass is 10%) to obtain a monofilament with a diameter of 0.2mm. Sulfuric acid (20g / L) is used as the electrolyte, and anodizing is performed for 10min to form an oxide film with a thickness of 2μm on the surface of the monofilament to enhance the interfacial bonding with epoxy resin, thereby obtaining an aluminum-magnesium alloy monofilament with a diameter of 0.204mm.

[0055] Step 2: Apply an epoxy resin containing nanoparticles to the surface of the reinforcing fiber layer by spraying, followed by step curing to form a second epoxy resin coating layer with a thickness of 80 μm on the surface of the reinforcing fiber layer (the second epoxy resin coating layer contains nanoparticles to enhance wear resistance), thus obtaining a carbon fiber / metal fiber composite reinforcing material. The step curing includes: curing at 120℃ for 2 hours at 0.7 MPa, followed by curing at 150℃ for 4 hours. The content of nanoparticles in the epoxy resin containing nanoparticles is 8 wt%, the epoxy resin is E-51, the nanoparticles are nano SiO2, and the particle size of the nanoparticles is 80 nm.

[0056] The tensile strength, interlaminar shear strength, and coefficient of thermal expansion of the multilayer laminate prepared in Example 1 and a conventional carbon fiber plate (purchased from Toho Carbon Fiber, model UM55) were tested. The test results are shown in Table 1. The multilayer laminate prepared in Example 1 was used as a high-strength laminate for aerospace applications.

[0057] Table 1

[0058]

[0059] Example 2

[0060] A method for preparing a multilayer laminate includes: stacking multiple carbon fiber / metal fiber composite reinforcement materials into 10 composite layers to obtain a multilayer laminate with a thickness of approximately 6 mm (density of 2.1 g / cm³). 3 During the stacking process, a second epoxy resin mixture is coated (sprayed) between adjacent composite layers. After curing (curing temperature is 140℃, pressure is 4MPa, curing time is 600min), an epoxy resin bonding layer with a thickness of 16μm is formed between adjacent composite layers. The second epoxy resin mixture is a mixture of bisphenol A type epoxy resin (E-44) and m-phenylenediamine. The concentration of m-phenylenediamine in the second epoxy resin mixture is 14wt%, the temperature of the second epoxy resin mixture is 40℃, the epoxy value of the epoxy resin (E-44) in the second epoxy resin mixture is 0.44eq / 100g, and the viscosity of the second epoxy resin mixture is 650mPa·s.

[0061] The preparation method of the above-mentioned carbon fiber / metal fiber composite reinforced material includes the following steps:

[0062] Step 1: On a CNC winding machine, two layers of inner composite filaments are wound onto the surface of the carbon fiber bundle to form a reinforcing fiber layer. During the winding process, the inner composite filaments exhibit a serpentine waveform on the carbon fiber bundle. The winding angle of the first inner composite filament is 60° (the winding direction of the inner composite filament is at 60° to the carbon fiber bundle). The difference in winding angle between the second inner composite filament and the first inner composite filament is 37°. The winding speed is 78 r / min. The carbon fiber bundle is T700-24k, and the diameter of the carbon fiber bundle is 100 μm.

[0063] The method for obtaining the inner composite filament includes: coating the outer surface of an aluminum-magnesium alloy monofilament with a first epoxy resin mixture by dip coating, specifically including: passing the aluminum-magnesium alloy monofilament through a tank containing the first epoxy resin mixture at a speed of 5 m / min, and then pre-curing it at 80℃ for 30 min to form a first epoxy resin coating layer with a thickness of 10 μm on the outer surface of the aluminum-magnesium alloy monofilament, thereby obtaining an inner composite filament with a thickness of 0.224 mm. The first epoxy resin mixture is a mixture of bisphenol A type epoxy resin (E-44) and m-phenylenediamine, the concentration of m-phenylenediamine in the first epoxy resin mixture is 14 wt%, the temperature of the first epoxy resin mixture in the tank is 40℃, the epoxy value of the epoxy resin (E-44) in the first epoxy resin mixture is 0.44 eq / 100 g, and the viscosity of the first epoxy resin mixture is 675 mPa·s.

[0064] The method for obtaining aluminum-magnesium alloy monofilaments includes: cold drawing 12 times (each time deformation is 15%) on an aluminum-magnesium alloy rod with a diameter of 15 mm (grade 5052, magnesium content in the aluminum-magnesium alloy rod is 2.5 wt%) to obtain a monofilament with a diameter of 0.2 mm; using sulfuric acid (20 g / L) as electrolyte, anodizing treatment is performed for 10 min to form an oxide film with a thickness of 2 μm on the surface of the monofilament, thus obtaining an aluminum-magnesium alloy monofilament with a diameter of 0.204 mm.

[0065] Step 2: Apply epoxy resin containing nanoparticles to the surface of the reinforcing fiber layer by spraying, followed by step curing to form a second epoxy resin coating layer with a thickness of 100 μm on the surface of the reinforcing fiber layer, thus obtaining the carbon fiber / metal fiber composite reinforcing material. The step curing includes: curing at 120℃ for 2 hours at 0.7 MPa, followed by curing at 150℃ for 4 hours. The content of nanoparticles in the epoxy resin containing nanoparticles is 10 wt%, the epoxy resin is E-44, the nanoparticles are nano SiO2, and the particle size of the nanoparticles is 50-100 nm.

[0066] The flexural strength, impact toughness, and temperature resistance of the multilayer laminate prepared in Example 2 and a traditional carbon fiber sheet (purchased from Toho Carbon Fiber, model UM55) were tested. The test results are shown in Table 2. The multilayer laminate prepared in Example 2 was used as a lightweight component for the automotive chassis.

[0067] Table 2

[0068]

[0069] The present invention has been described above by way of example. It should be noted that any simple modifications, alterations or other equivalent substitutions that can be made by those skilled in the art without creative effort without departing from the core of the present invention fall within the protection scope of the present invention.

Claims

1. A carbon fiber / metal fiber composite reinforced material, characterized in that, include: A carbon fiber bundle has a reinforcing fiber layer covering its outer surface, and a second epoxy resin coating layer covering its outer surface. The reinforcing fiber layer is formed by an inner composite filament wound around the surface of the carbon fiber bundle. The inner composite filament includes an aluminum-magnesium alloy monofilament and a first epoxy resin coating layer covering the outer surface of the aluminum-magnesium alloy monofilament. The second epoxy resin coating layer contains nanoparticles with a particle size of 50-100 nm, and the nanoparticles are nano-SiO2. An oxide film with a thickness of 1 to 3 μm is formed on the outer surface of the aluminum-magnesium alloy monofilament, which is formed by anodic oxidation. An epoxy resin containing nanoparticles is coated on the surface of the reinforcing fiber layer and cured in stages to form a second epoxy resin coating layer on the surface of the reinforcing fiber layer. The content of nanoparticles in the epoxy resin containing nanoparticles is 5-10 wt%. The inner composite filaments are wound in a periodic S-shaped or serpentine waveform on the carbon fiber bundle, with a winding angle of 30° to 60° and a difference of ≥15° between the winding angles of two adjacent inner composite filaments.

2. The carbon fiber / metal fiber composite reinforced material according to claim 1, characterized in that, The thickness of the second epoxy resin coating layer is 50~100μm.

3. The carbon fiber / metal fiber composite reinforced material according to claim 1, characterized in that, The diameter of the aluminum-magnesium alloy monofilament is 0.1~0.3mm, and the thickness of the first epoxy resin coating layer is 5~15μm. The first epoxy resin coating layer includes epoxy resin.

4. The carbon fiber / metal fiber composite reinforced material according to claim 1, characterized in that, The diameter of the carbon fiber bundles ranges from 1 to 200 μm.

5. The carbon fiber / metal fiber composite reinforced material according to claim 1, characterized in that, The method for obtaining the inner composite filament includes: coating the outer surface of the aluminum-magnesium alloy monofilament with a first epoxy resin mixture, pre-curing it, and forming a first epoxy resin coating layer on the outer surface of the aluminum-magnesium alloy monofilament to obtain the inner composite filament.

6. The method for preparing the carbon fiber / metal fiber composite reinforced material as described in claim 1, characterized in that, Includes the following steps: Step 1: Wind 1 to 10 layers of the inner composite filaments onto the surface of the carbon fiber bundle to obtain a reinforcing fiber layer on the surface of the carbon fiber bundle; Step 2: Coat the surface of the reinforcing fiber layer with epoxy resin containing nanoparticles, and cure in stages to form a second epoxy resin coating layer on the surface of the reinforcing fiber layer, thereby obtaining a carbon fiber / metal fiber composite reinforcing material.

7. A multi-layered laminated board, characterized in that, include: The composite layer consists of 5 to 50 layers arranged in a layered manner, with an epoxy resin bonding layer connecting adjacent composite layers. Each composite layer is composed of multiple parallel carbon fiber / metal fiber composite reinforcing materials as described in claim 1 arranged in a close-packed manner.

8. A method for preparing a multilayer laminate, characterized in that, include: Multiple carbon fiber / metal fiber composite reinforcing materials as described in claim 1 are stacked into multilayer composite layers to obtain a multilayer structure laminate. During the stacking process, a second epoxy resin mixture is coated between adjacent composite layers. After curing, an epoxy resin bonding layer is formed between adjacent composite layers. The second epoxy resin mixture includes epoxy resin.

9. The application of the multilayer laminate as described in claim 7 in improving tensile strength, interlaminar shear strength, coefficient of thermal expansion, flexural strength, or impact toughness.

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