Metal carbon fiber composite material and preparation method thereof

Abstract

The invention relates to a metal carbon fiber composite material and a preparation method thereof, the composite material comprises thermoplastic resin, thermosetting resin and an energy absorbing material, and the weight ratio of the thermoplastic resin to the thermosetting resin to the energy absorbing material is 1: (0.05-0.1): (0.2-0.8); the energy-absorbing material comprises foam metal, carbon fiber and foaming resin in a weight ratio of 1: (0.5-1.5): (0.1-0.5); the method comprises the following steps: placing foam metal in a polymer solution, drying, and coating a nano material to obtain a mixture A; placing the mixture A in carbon fibers, and then placing the mixture A in foaming resin for mixing to obtain a mixture B; thermosetting resin and thermoplastic resin are mixed and placed in the mixture B to obtain a mixture C, the mixture C is heated to be molten, and the composite material is obtained after hot pressing and cooling. The low-density and high-strength foam metal and the carbon fibers are compounded, so that the heat transfer performance is good, and the electromagnetic shielding effect is good; the bonding resin and the carbon fiber material are high in bonding strength and have better shock absorption and energy absorption performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite materials, in particular to the technical field of carbon fiber composite materials, and specifically relates to a metal carbon fiber composite material and a preparation method thereof. Background Art

[0002] Porous metal has many excellent properties and is a new type of engineering material. The structural characteristic of porous metal is that it contains more pores. Compared with ordinary metals, porous metals are more easily deformed when subjected to stress, thereby absorbing more energy. Generally speaking, the presence of bubbles in metals will cause structural defects, resulting in stress concentration at the defects when the metal is subjected to stress, and will also change the physical, chemical and other properties of the porous metal, thereby affecting its service life and scope of use. However, if the number of pores is large and widely distributed, the metal material will acquire new structural properties under the influence of the pores. These properties usually include low density, high specific strength, good shock absorption, high energy absorption, excellent sound insulation, high electromagnetic shielding efficiency, etc.

[0003] While metal foam has numerous advantages, it also has significant disadvantages. Its inherent strength is still relatively low compared to aluminum blocks of the same volume, which greatly limits its application. To improve the performance of aluminum foam, filling its pores with polymers is an effective method for enhancing its strength. This method combines the excellent properties of polymers with aluminum foam to form an interpenetrating composite material.

[0004] Refer to the patent publication number CN105603248A, which discloses a foam graphene skeleton reinforced copper-based composite material and a preparation method. The composite material consists of a foam substrate, a graphene reinforcement layer, and a matrix material. The foam substrate is foam metal, foam ceramic, or foam carbon. The graphene reinforcement layer is a graphene film or a composite of graphene and diamond or carbon nanotubes. The matrix material is copper and copper alloy. However, the patent provides ceramic foam with certain electrical and thermal conductivity by depositing a metal base layer, and does not take into account the bonding force between the metal layer and the ceramic layer. As a result, the composite material has a limited lifespan.

[0005] Referring to the patent with publication number CN108358185A, a method for preparing a toughened high thermal conductivity carbon foam is disclosed, which comprises immersing a loofah cotton body in a homemade suspension to obtain a polytetrafluoroethylene-loaded loofah cotton body, dripping aluminum melt into the loofah cotton body, placing the aluminum-filled loofah cotton body into a muffle furnace to obtain a filamentous aluminum foam template, using the filamentous aluminum foam template as an anode, electrolytically oxidizing to obtain an anodized aluminum foam template, mixing expanded graphite acid solution, asphalt, and epoxy resin to obtain a mixed resin, pouring the mixed resin melt onto the anodized aluminum foam template to obtain a carbon foam preform, and placing the carbon foam preform into a tubular furnace to obtain a toughened high thermal conductivity carbon foam. The preparation method of this patent is highly complex, and the mechanical properties and thermal conductivity of the carbon foam are poor, and the low porosity of the carbon foam cannot enhance the thermal and electrical conductivity of the metal foam. Summary of the Invention

[0006] An object of the present invention is to provide a composite material, in particular a metal carbon fiber composite material with high specific strength, good shock absorption effect and high electromagnetic shielding efficiency.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is:

[0008] A metal carbon fiber composite material comprises a thermoplastic resin, a thermosetting resin, and an energy-absorbing material, wherein the weight ratio of the thermoplastic resin, the thermosetting resin, and the energy-absorbing material is 1:0.05-0.1:0.2-0.8;

[0009] The energy absorbing material comprises foam metal, carbon fiber and foam resin, and the weight ratio of the foam metal, carbon fiber and foam resin is 1:0.5-1.5:0.1-0.5.

[0010] Preferably, the above technical solution comprises one or more of foamed aluminum, foamed nickel, foamed copper, foamed magnesium, foamed titanium, foamed iron, and foamed silver. The foamed metal bubble is a new type of porous metal material with unique structure and performance. Its core feature is the large number of pores evenly distributed in the metal matrix, which makes the material have the characteristics of light weight, high specific strength, energy absorption and buffering, thermal conductivity and electrical conductivity. It retains the traditional properties of metal such as ductility and conductivity, and has the functions of energy absorption and vibration reduction, sound insulation and noise reduction, and electromagnetic shielding of porous materials.

[0011] Further preferably, the foam metal is one or both of foam aluminum and foam nickel, which have better affinity with the resin material.

[0012] Preferably, in the above technical solution, the metal porosity of the foam metal is 30% to 95%. The porosity of the foam metal refers to the percentage of the pore volume in the foam metal material to the total volume of the material in its natural state. The porosity is tested in accordance with GB / T10799-2008 standard.

[0013] Further preferably, the metal porosity of the foam metal is 50% to 95%. If the porosity is small, the pore volume in the material is small, which can easily cause the density of the composite material to be large, the lightness and shock absorption performance to be not improved. If the porosity is large, it can easily cause insufficient filling and reduced heat transfer.

[0014] Preferably, in the above technical solution, the average pore size of the foam metal is 1 to 10 mm, and the average pore size of the foam metal is the cross-sectional diameter of the pores in the foam metal, which is measured by photographing the cross section with a scanning electron microscope.

[0015] Further preferably, the average pore size of the foam metal is 1 to 5 mm to obtain better electromagnetic shielding efficiency and thermal conductivity.

[0016] Preferably, the above technical solution is that the foam metal is modified by chemical oxidation, plasma treatment or nanomaterial modification. Considering the adhesion between the foam metal and the carbon fiber, and the adhesion with the foaming resin, the shock resistance and service life of the composite material are improved, and the foam metal needs to be modified.

[0017] Further preferably, the foam metal is modified by a nanomaterial modification method to improve the convenience of the operation process.

[0018] Further preferably, the nanomaterial comprises one or more of nano-titanium dioxide, nano-silicon dioxide, nano-silver, and carbon fiber nanotubes.

[0019] More preferably, the nanomaterial package is one or both of nano-silicon dioxide and carbon fiber nanotubes to improve the bonding strength.

[0020] Preferably, the above technical solution comprises carbon fiber powder, chopped carbon fiber, chopped carbon fiber, carbon fiber filament, and carbon fiber cloth. The carbon fiber is mainly composed of carbon element, has light weight, excellent conductivity, and can absorb and attenuate electromagnetic energy propagation between the shielding area and the outside world.

[0021] Further preferably, the carbon fiber is carbon fiber powder to obtain better electromagnetic shielding efficiency, thermal conductivity and heat dissipation, and at the same time to simplify the preparation process and facilitate embedding in porous metal materials.

[0022] More preferably, the average length of the carbon fiber powder is 10-200 μm.

[0023] Still more preferably, the average length of the carbon fiber powder is 10-100 μm, so as to be better embedded in the porous metal material.

[0024] Preferably, in the above technical solution, the foamed resin comprises one or more of polystyrene, polyurethane, polyvinyl chloride, and polyethylene. The foamed resin is a material that is processed through a specific process to produce a microporous structure of the resin. These microporous structures give the material properties such as lightness, heat insulation, sound absorption, and shock absorption.

[0025] Further preferably, the foaming resin is one or both of polyethylene and polyurethane to obtain better stability and energy absorption performance.

[0026] In the above technical solution, preferably, the thermoplastic resin comprises one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamide, polyoxymethylene, polycarbonate, polyphenylene ether, polysulfone, rubber, and polyester.

[0027] Further preferably, the thermoplastic resin is polyamide to obtain high strength and service life. The polyamide is a polymer material containing an amide group (-CO-NH-) repeating structural unit, which can be an aliphatic polyamide: polybutylene adipamide, polyhexamethylene adipamide, polyhexamethylene sebacamide, polydodecane diamide, polyhexamethylene sebacamide; semi-aromatic polyamide: polybutylene terephthalamide, polybutylene furan diamide, polypentamethylene terephthalamide, polypentamethylene furan diamide, polyhexamethylene terephthalamide, polyhexamethylene furan diamide, polynonamethylene terephthalamide Diamine, poly(nonanediamine furandiamide), poly(decane terephthalamide), poly(decanediamine furandiamide), poly(dodecanediamine furandiamide), poly(tridecanediamine furandiamide), poly(tridecanediamine furandiamide), poly(hexamethylenediamine adipate terephthalamide decanediamine), poly(furandicarboxamide terephthalate decanediamine), poly(pentamethylenediamine furandiamide terephthalate), poly(furandicarboxamide terephthalate decanediamine); it can also be an aromatic polyamide: poly(p-phenylene terephthalamide), poly(p-phenylene furandiamide), poly(p-phenylene terephthalate furandiamide).

[0028] More preferably, the polyamide is a semi-aromatic polyamide to obtain better temperature resistance and low water absorption rate to maintain a long service life of the composite material.

[0029] Still more preferably, the semi-aromatic polyamide is the thermoplastic resin and is one or both of polydecanediamine terephthalate and polyhexamethylenediamine furandicarboxylate.

[0030] Preferably, the above technical solution comprises one or more of thermosetting epoxy resin, thermosetting unsaturated polyester resin, thermosetting polyurethane resin, thermosetting phenolic resin, thermosetting urea-formaldehyde resin, thermosetting silicone resin, and thermosetting melamine-formaldehyde resin. The thermosetting resin has a large number of polar groups and is used for bonding foam metal, carbon fiber powder, and thermoplastic resin.

[0031] Further preferably, the thermosetting resin is a thermosetting unsaturated polyester resin to ensure the excellent strength of the composite material. The unsaturated polyester resin is a polymer compound with a multifunctional group, with polyester chain bonds and unsaturated double bonds on its backbone, and carboxyl and hydroxyl groups at both ends of the macromolecular chain. It has high specific strength, good corrosion resistance and chemical resistance.

[0032] More preferably, the thermosetting unsaturated polyester resin is one or both of bisphenol A type vinyl unsaturated polyester and isophthalic acid type vinyl unsaturated resin, so that the prepared composite material has better mechanical properties, temperature resistance and corrosion resistance, thereby enhancing the service life of the composite material.

[0033] Another object of the present invention is to provide a method for preparing the metal carbon fiber composite material.

[0034] In order to achieve the above object, the technical solution adopted by the present invention is:

[0035] A method for preparing a metal carbon fiber composite material comprises the following steps:

[0036] (1) Preparing mixture A: placing a foamed metal in a polymer solution for ultrasonic vibration, taking it out and drying it, and coating the surface of the foamed metal with nanomaterials to obtain mixture A;

[0037] (2) Preparing mixture B: Mixture A is made into powder and then placed in carbon fiber for ultrasonic vibration, and then placed in molten foaming resin for thorough mixing to obtain mixture B;

[0038] (3) Preparation of composite materials: A thermosetting resin and a thermoplastic resin are mixed and placed in a mixture B, heated and stirred to obtain a mixture C, and the mixture C is heated until it is melted, hot-pressed, and cooled to obtain a composite material.

[0039] Preferably, in the above technical solution, the polymer solution comprises one or both of a polyacrylamide solution and a polyvinyl alcohol solution.

[0040] More preferably, the polymer solution is a polyacrylamide solution.

[0041] Preferably, in the above technical solution, in (1): the frequency of the ultrasonic vibration is 25 to 45 Hz, and the duration is 15 to 45 minutes.

[0042] Preferably, in the above technical solution, in (2): the frequency of the ultrasonic vibration is 20 to 120 kHz, and the duration is 10 to 60 minutes.

[0043] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0044] 1. The composite material of the present invention is a composite of low-density and high-strength foam metal and carbon fiber, which has good heat transfer performance and electromagnetic shielding effect;

[0045] 2. The composite material of the present invention uses modified foam metal as a base material, bonded with resin and carbon fiber materials, has high bonding strength, and has better shock absorption and energy absorption performance. DETAILED DESCRIPTION

[0046] The technical solution of the present invention will be described clearly and completely below. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0047] The raw materials used in each embodiment and comparative example are as follows:

[0048] Metal foam

[0049] A1: Foam aluminum, TMAX-Aluminumfoam-02 foam aluminum produced by Xiamen Tianmeifu Machinery Equipment Co., Ltd., with a porosity of 68-78%, an average pore size of 1.6mm, and crushed and sieved to 20 mesh.

[0050] A2: Nickel foam, TMAX-NickelFoam-02 nickel foam produced by Xiamen Tianmeifu Machinery Equipment Co., Ltd., with a porosity of 85-93%, an average pore size of 0.8mm, and crushed and sieved to 20 mesh.

[0051]

Carbon fiber

[0052] B1: MLD-30, carbon fiber powder produced by Toray Industries, Ltd. of Japan, with a fiber length of 30μm.

[0053] B2: MLD-300, carbon fiber powder produced by Toray Industries, Ltd. of Japan, with a fiber length of 130μm.

[0054]

Foaming resin

[0055] C1: Polyethylene, LD100AC polyethylene produced by Sinopec Shanghai Petrochemical Co., Ltd.

[0056] C2: Polyurethane, FP3039D6 polyether polyurethane produced by GreenMobil.

[0057]

Thermosetting resin

[0058] D: Bisphenol A type vinyl unsaturated polyester, produced by Jinan Changhua Resin Chemical Co., Ltd.

[0059]

Thermoplastic resin

[0060] E1: Polydecane terephthalate, VicnylPA10T produced by Kingfa Science & Technology Co., Ltd.

[0061] E2: Poly(hexamethylene furandicarboxylic acid), produced by Zhongke Guosheng (Lishui) New Materials Technology Co., Ltd.

[0062] Nanomaterials

[0063] F1: Nano-silica, S104596 nano-silica produced by Aladdin Reagent Company.

[0064] F2: Carbon fiber nanotubes, C313046 carbon fiber nanotubes produced by Aladdin Reagent Company.

[0065] Polymer solution

[0066] G: Polyacrylamide solution, P754432 polyacrylamide produced by Aladdin Reagent Company, a polymer solution with a solid content of 30 wt%.

[0067] Table 1:

[0068]

[0069] Mixture A (M1-M4) was prepared according to the formula shown in Table 1: the foamed metal was placed in a polymer solution and ultrasonically vibrated at a frequency of 30 Hz. After ultrasonic vibration for 30 minutes, it was taken out and dried. The nanomaterial was coated on the surface of the foamed metal by a spraying process to obtain mixture A.

[0070] Mixture A (M5): Mixture A is obtained by coating the surface of the foam metal with nanomaterials through a spraying process.

[0071] Table 2:

[0072]

[0073]

[0074] Mixture B (N1-N11) was prepared according to the formula shown in Table 2. Mixture A was made into powder and placed in carbon fiber for ultrasonic vibration at a frequency of 70 kHz. After ultrasonic vibration for 35 minutes, it was placed in molten foaming resin and fully mixed to obtain mixture B.

[0075] Mixture B (N12): Mixture A was made into powder and then placed in carbon fiber for ultrasonic vibration at a frequency of 70 kHz. Mixture B was obtained after ultrasonic vibration for 35 minutes.

[0076] Table 3:

[0077]

[0078] Prepare a composite material according to Table 3: Prepare a composite material: mix the thermosetting resin and the thermoplastic resin and place them in the mixture B, heat and stir to obtain the mixture C, heat the mixture C until it is melted, hot press and cool to obtain the composite material.

[0079] The following tests were conducted on the composite materials. Unless otherwise specified, all tests were conducted at 25°C. The main indicators are as follows:

[0080] 1. Destructive impact strength: refer to ASTM D7136-2007 and use Instron 9350 fully automatic drop hammer impact tester for testing. The total mass of the drop hammer is 1±0.05kg, the diameter of the impact head is 3±0.1mm, and each group of samples starts the test with a kinetic energy of 100J and increases in a gradient of 10J until the sample is destroyed to obtain the destructive impact strength of the sample.

[0081] 2. Tensile strength: Tested according to GB / T1040.1-2018, the specimen was stretched at a rate of 5 mm / min, and the specimen size was 100 mm × 10 mm.

[0082] 3. Average electromagnetic shielding effectiveness: tested in accordance with GB / T30142-2013 standard, the test frequency range is 8~12GHz.

[0083] 4. Thermal conductivity: Tested in accordance with the national standard GB / T10297-2015, the sample size is 40mm×80mm×120mm, the thermocouple measurement spacing is 60mm, and the heating power is 2KW / h.

[0084] Table 4:

[0085]

[0086] As shown in Table 4, compared with the comparative example, the composite materials prepared in the examples have better electromagnetic shielding effectiveness and thermal conductivity, with average electromagnetic shielding effectiveness above 46 dB and thermal conductivity above 280 W / (m·K); excellent mechanical properties, and the destructive impact strength is greater than 58 J / mm 2 , the tensile strength is greater than 158Mpa; the preparation process of the composite material prepared in the embodiment is simple and convenient, the preparation process is pollution-free, and it is easy to produce on a large scale.

[0087] The above embodiments are intended only to illustrate the technical concepts and features of the present invention. Their purpose is to enable those skilled in the art to understand the contents of the present invention and implement them accordingly. They are not intended to limit the scope of protection of the present invention. Any equivalent changes or modifications made in accordance with the spirit of the present invention are intended to be covered by the scope of protection of the present invention.

Claims

1. A metal carbon fiber composite material, characterized in that: The invention comprises a thermoplastic resin, a thermosetting resin and an energy absorbing material, wherein the weight ratio of the thermoplastic resin, the thermosetting resin and the energy absorbing material is 1:0.05-0.1:0.2-0.8; The energy absorbing material comprises foam metal, carbon fiber and foam resin, and the weight ratio of the foam metal, carbon fiber and foam resin is 1:0.5-1.5:0.1-0.

5.

2. The metal carbon fiber composite material according to claim 1, characterized in that: The foam metal comprises one or more of foam aluminum, foam nickel, foam copper, foam magnesium, foam titanium, foam iron, and foam silver; The foaming resin includes one or more of polystyrene, polyurethane, polyvinyl chloride and polyethylene.

3. The metal-carbon fiber composite material according to claim 2, characterized in that: The foam metal is one or both of foam aluminum and foam nickel; The foaming resin is one or both of polyethylene and polyurethane.

4. The metal-carbon fiber composite material according to claim 1, characterized in that: The metal porosity of the foam metal is 30% to 95%; The average pore diameter of the foam metal is 1 to 10 mm; The average length of the carbon fibers is 10-200 μm.

5. The metal carbon fiber composite material according to claim 1, characterized in that: The foam metal is modified by chemical oxidation, plasma treatment or nanomaterial modification, and the nanomaterial comprises one or more of nano-titanium dioxide, nano-silicon dioxide, nano-silver and carbon fiber nanotubes.

6. The metal-carbon fiber composite material according to claim 1, characterized in that: The thermoplastic resin comprises one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamide, polyoxymethylene, polycarbonate, polyphenylene ether, polysulfone, rubber, and polyester; The thermosetting resin includes one or more of thermosetting epoxy resin, thermosetting unsaturated polyester resin, thermosetting polyurethane resin, thermosetting phenolic resin, thermosetting urea-formaldehyde resin, thermosetting silicone resin, and thermosetting melamine-formaldehyde resin.

7. The metal-carbon fiber composite material according to claim 1, characterized in that: The thermoplastic resin is one or both of polydecanediamine terephthalate and polyhexamethylenediamine furandicarboxylate; The thermosetting resin is one or both of bisphenol A type vinyl unsaturated polyester and isophthalic acid type vinyl unsaturated resin.

8. A method for preparing the metal-carbon fiber composite material according to any one of claims 1 to 7, characterized in that: The following steps are involved: (1) Preparing mixture A: placing a foamed metal in a polymer solution for ultrasonic vibration, taking it out and drying it, and coating the surface of the foamed metal with nanomaterials to obtain mixture A; (2) Preparing mixture B: Mixture A is made into powder and then placed in carbon fiber for ultrasonic vibration, and then placed in molten foaming resin for thorough mixing to obtain mixture B; (3) Preparation of composite materials: A thermosetting resin and a thermoplastic resin are mixed and placed in a mixture B, heated and stirred to obtain a mixture C, and the mixture C is heated until it is melted, hot-pressed, and cooled to obtain a composite material.

9. The preparation method according to claim 8, characterized in that: The polymer solution comprises one or both of polyacrylamide solution and polyvinyl alcohol solution.

10. The preparation method according to claim 8, characterized in that: In (1): the frequency of ultrasonic vibration is 25 Hz to 45 Hz, and the duration is 15 to 45 min; In (2): the frequency of ultrasonic vibration is 20 to 120 kHz, and the duration is 10 to 60 minutes.

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