High performance composite material and method for making same

Abstract

The application relates to the technical field of ablation-resistant materials, in particular to a high-performance composite material and a preparation method thereof, which comprises the following steps: surface modification of coated carbon fibers and carbon nanotubes by using silane coupling agents respectively to obtain modified carbon fibers and modified carbon nanotubes; uniform stirring of polyphenyl ether resin, an antioxidant, anti-precipitation flame-retardant microspheres and the modified carbon nanotubes to obtain a mixture; side feeding of the modified carbon fibers in a double-screw extruder, extrusion granulation and preparation of the high-performance composite material. By adding the coated carbon fibers, the anti-precipitation flame-retardant microspheres and the carbon nanotubes in the resin matrix, the ablation resistance and the friction resistance of the prepared composite material are greatly improved; specifically, the zirconium oxide film is coated on the surface of the carbon fibers, the coated carbon fibers have the characteristics of high-temperature oxidation resistance, corrosion resistance and high hardness, and the coated carbon fibers and the carbon nanotubes jointly act, so that the overall performance of the composite material is enhanced.

Description

Technical Field

[0001] This invention relates to the field of ablation-resistant materials technology, specifically to a high-performance composite material and its preparation method. Background Technology

[0002] Polyphenylene oxide (PPE) resin is a high-performance engineering plastic renowned for its excellent electrical insulation, high-temperature resistance, and dimensional stability. It is widely used in the manufacture of electronic, automotive, and home appliance components. The use of PPE resin as a matrix in the manufacture of power battery casings is also becoming increasingly common. Adding fillers and flame retardants to polyphenylene ether resin can significantly improve the ablation resistance of the matrix material. However, due to the poor compatibility between flame retardants and polyphenylene ether resin, the interfacial forces are insufficient, making the flame retardants prone to migration or partial aggregation to the resin matrix surface driven by van der Waals forces. This not only affects the appearance of the finished product but also severely impacts its ablation resistance. Therefore, this paper proposes a high-performance composite material and its preparation method. Summary of the Invention

[0003] To address the shortcomings of existing technologies, this invention provides a high-performance composite material and its preparation method. By adding coated carbon fibers, flame-retardant microspheres that prevent exudation, and carbon nanotubes to a resin matrix, the ablation resistance and abrasion resistance of the prepared composite material are significantly improved.

[0004] To achieve the above objectives, the present invention provides the following technical solution: a high-performance composite material comprising the following raw materials in parts by weight: 120-150 parts of polyphenylene ether resin, 1-3 parts of antioxidant, 10-15 parts of coated carbon fiber, 15-20 parts of anti-exudation flame-retardant microspheres, and 5-10 parts of carbon nanotubes.

[0005] Preferably, the antioxidant is selected from antioxidant 1010, antioxidant DLTP and antioxidant 168.

[0006] Preferably, the preparation method of the coated carbon fiber is as follows: S11, dissolve zirconium acetylacetonate in N,N-dimethylformamide, heat and stir until clear and transparent to obtain a zirconium oxide precursor solution; S12, ultrasonically disperse carbon fiber in the zirconium oxide precursor solution, stir continuously and then separate, and treat with ultraviolet light to form a zirconium oxide film on the surface of the carbon fiber, thereby obtaining the coated carbon fiber.

[0007] Preferably, in step S11, the heating and stirring temperature is 90-95°C; the mass ratio of zirconium acetylacetonate to N,N-dimethylformamide is 1:(10-12).

[0008] Preferably, in step S12, the continuous stirring time is 1.5-2 hours; the ultraviolet irradiation treatment time is 1.2-1.5 hours.

[0009] Preferably, the preparation method of the flame-retardant microspheres is as follows: S21, dissolve ammonium polyphosphate in deionized water to obtain a flame-retardant solution; S22, immerse porous polystyrene microspheres in the flame-retardant solution, separate them after pressure treatment, and then dry them. Repeat the immersion and drying process more than 3 times to obtain flame-retardant microspheres.

[0010] Preferably, in step S21, the ratio of ammonium polyphosphate to deionized water is 1:(5-8)g / mL.

[0011] Preferably, in step S22, the pressurization process is carried out at 1-1.5 MPa for 2-3 hours.

[0012] This invention also provides a method for preparing a high-performance composite material, comprising the following steps: (1) Silane coupling agent was used to modify the surface of coated carbon fibers and carbon nanotubes respectively to obtain modified carbon fibers and modified carbon nanotubes. (2) The polyphenylene ether resin, antioxidant, flame-retardant microspheres and modified carbon nanotubes are stirred evenly to obtain a mixture; (3) The mixture is fed into a twin-screw extruder to side-feed the modified carbon fiber, and then extruded and granulated to obtain a high-performance composite material.

[0013] Preferably, in step (1), the silane coupling agent is selected from KH-550 and KH-560.

[0014] This invention provides a high-performance composite material and its preparation method, which has the following advantages compared with the prior art: This invention significantly improves the ablation resistance and abrasion resistance of the prepared composite material by adding coated carbon fibers, anti-exudation flame-retardant microspheres, and carbon nanotubes to the resin matrix. Specifically, a zirconium oxide film is coated on the surface of the carbon fibers, which has the characteristics of high temperature oxidation resistance, corrosion resistance, and high hardness. Combined with the nanotubes, the overall performance of the composite material can be enhanced.

[0015] This invention loads ammonium polyphosphate flame retardant into the pores of porous polystyrene microspheres, solving the problem of poor compatibility between ammonium polyphosphate flame retardant and polyphenylene ether resin matrix when in direct contact. It effectively prevents the ammonium polyphosphate flame retardant from migrating to the matrix surface and reducing or losing its flame retardant effect, ensuring that the composite material still has excellent ablation resistance after long-term use. Attached Figure Description

[0016] The accompanying drawings, which are included to provide a further understanding of this application and form part of this application, illustrate exemplary embodiments and are used to explain this application, but do not constitute an undue limitation of this application. In the drawings: Figure 1These are surface views of aging sample A and aging sample B in this invention. Figure 2 The images show the ablation treatment of the sample in Example 6, the sample in Comparative Example 2, and the aged sample B in this invention. Detailed Implementation

[0017] The following embodiments are provided to illustrate the implementation of this application in detail, so that the process of how this application uses technical means to solve technical problems and achieve technical effects can be fully understood and implemented accordingly.

[0018] Example 1 The preparation method of coated carbon fiber is as follows: S11. Dissolve zirconium acetylacetonate in N,N-dimethylformamide at a mass ratio of 1:12, and stir at 90°C until clear and transparent to obtain a zirconium oxide precursor solution. S12. The carbon fiber is ultrasonically dispersed in a zirconia precursor solution, stirred continuously for 2 hours, and then separated. After being treated with ultraviolet light for 1.2 hours, a zirconia film is formed on the surface of the carbon fiber, thus obtaining the coated carbon fiber.

[0019] Example 2 The preparation method of coated carbon fiber is as follows: S11. Dissolve zirconium acetylacetonate in N,N-dimethylformamide at a mass ratio of 1:10, and stir at 95°C until clear and transparent to obtain a zirconium oxide precursor solution. S12. The carbon fiber is ultrasonically dispersed in a zirconia precursor solution and stirred continuously for 1.5 hours before separation. After being treated with ultraviolet light for 1.5 hours, a zirconia film is formed on the surface of the carbon fiber, thus obtaining the coated carbon fiber.

[0020] Example 3 The preparation method of the anti-precipitation flame-retardant microspheres is as follows: S21. Dissolve ammonium polyphosphate in deionized water at a material-to-liquid ratio of 1:8 g / mL to obtain a flame-retardant solution; S22. Porous polystyrene microspheres are immersed in a flame retardant solution, kept under pressure at 1 MPa for 3 hours, separated, and then dried. The immersion and drying are repeated 3 times to obtain flame retardant microspheres that prevent precipitation.

[0021] Example 4 The preparation method of the anti-precipitation flame-retardant microspheres is as follows: S21. Dissolve ammonium polyphosphate in deionized water at a material-to-liquid ratio of 1:5 g / mL to obtain a flame-retardant solution; S22. Porous polystyrene microspheres are immersed in a flame retardant solution, held at 1.5 MPa for 2 hours, separated, and then dried. The immersion and drying process is repeated 4 times to obtain flame retardant microspheres that prevent precipitation.

[0022] Example 5 A high-performance composite material comprises the following raw materials in parts by weight: 150 parts of polyphenylene ether resin, 1 part of antioxidant 168, 15 parts of coated carbon fiber, 15 parts of anti-exudation flame-retardant microspheres, and 10 parts of carbon nanotubes.

[0023] The preparation method of the above-mentioned high-performance composite material includes the following steps: (1) Surface modification of coated carbon fibers and carbon nanotubes was carried out using silane coupling agent KH-550 to obtain modified carbon fibers and modified carbon nanotubes. (2) The polyphenylene ether resin, antioxidant, flame-retardant microspheres and modified carbon nanotubes are stirred evenly to obtain a mixture; (3) The mixture is fed into a twin-screw extruder to side-feed the modified carbon fiber, and then extruded and granulated to obtain a high-performance composite material.

[0024] In this embodiment, the coated carbon fiber from Example 1 and the flame-retardant microspheres for preventing exudation from Example 3 are used.

[0025] Example 6 A high-performance composite material comprises the following raw materials in parts by weight: 135 parts of polyphenylene ether resin, 2 parts of antioxidant DLTP, 12 parts of coated carbon fiber, 18 parts of anti-exudation flame-retardant microspheres, and 7 parts of carbon nanotubes.

[0026] The preparation method of the above-mentioned high-performance composite material includes the following steps: (1) Surface modification of coated carbon fibers and carbon nanotubes was carried out using silane coupling agent KH-560 to obtain modified carbon fibers and modified carbon nanotubes. (2) The polyphenylene ether resin, antioxidant, flame-retardant microspheres and modified carbon nanotubes are stirred evenly to obtain a mixture; (3) The mixture is fed into a twin-screw extruder to side-feed the modified carbon fiber, and then extruded and granulated to obtain a high-performance composite material.

[0027] In this embodiment, the coated carbon fiber from Example 2 and the flame-retardant microspheres for preventing exudation from Example 4 are used.

[0028] Example 7 A high-performance composite material comprises the following raw materials in parts by weight: 120 parts of polyphenylene ether resin, 3 parts of antioxidant 1010, 10 parts of coated carbon fiber, 20 parts of anti-exudation flame-retardant microspheres, and 5 parts of carbon nanotubes.

[0029] The preparation method of the above-mentioned high-performance composite material includes the following steps: (1) Surface modification of coated carbon fibers and carbon nanotubes was carried out using silane coupling agent KH-560 to obtain modified carbon fibers and modified carbon nanotubes. (2) The polyphenylene ether resin, antioxidant, flame-retardant microspheres and modified carbon nanotubes are stirred evenly to obtain a mixture; (3) The mixture is fed into a twin-screw extruder to side-feed the modified carbon fiber, and then extruded and granulated to obtain a high-performance composite material.

[0030] In this embodiment, the coated carbon fiber from Example 1 and the flame-retardant microspheres for preventing exudation from Example 3 are used.

[0031] Comparative Example 1 A high-performance composite material comprises the following raw materials in parts by weight: 135 parts of polyphenylene ether resin, 2 parts of antioxidant DLTP, 12 parts of coated carbon fiber, 18 parts of ammonium polyphosphate flame retardant, and 7 parts of carbon nanotubes.

[0032] The preparation method of the above-mentioned high-performance composite material includes the following steps: (1) Surface modification of coated carbon fibers and carbon nanotubes was carried out using silane coupling agent KH-560 to obtain modified carbon fibers and modified carbon nanotubes. (2) The polyphenylene ether resin, antioxidant, ammonium polyphosphate flame retardant and modified carbon nanotubes are stirred evenly to obtain a mixture; (3) The mixture is fed into a twin-screw extruder to side-feed the modified carbon fiber, and then extruded and granulated to obtain a high-performance composite material.

[0033] In this comparative example, the coated carbon fiber from Example 2 is used.

[0034] Comparative Example 2 A high-performance composite material comprises the following raw materials in parts by weight: 135 parts of polyphenylene ether resin, 2 parts of antioxidant DLTP, 12 parts of carbon fiber, 18 parts of flame-retardant microspheres that prevent exudation, and 7 parts of carbon nanotubes.

[0035] The preparation method of the above-mentioned high-performance composite material includes the following steps: (1) Silane coupling agent KH-560 was used to modify the surface of carbon fibers and carbon nanotubes respectively to obtain modified carbon fibers and modified carbon nanotubes. (2) The polyphenylene ether resin, antioxidant, flame-retardant microspheres and modified carbon nanotubes are stirred evenly to obtain a mixture; (3) The mixture is fed into a twin-screw extruder to side-feed the modified carbon fiber, and then extruded and granulated to obtain a high-performance composite material.

[0036] In this comparative example, the flame-retardant microspheres for preventing exudation were used as described in Example 4.

[0037] Comparative Example 3 A high-performance composite material comprises the following raw materials in parts by weight: 135 parts of polyphenylene ether resin, 2 parts of antioxidant DLTP, 12 parts of coated carbon fiber, and 18 parts of anti-exudation flame-retardant microspheres.

[0038] The preparation method of the above-mentioned high-performance composite material includes the following steps: (1) Surface modification of coated carbon fibers was carried out using silane coupling agent KH-560 to obtain modified carbon fibers; (2) The polyphenylene ether resin, antioxidant and anti-precipitation flame retardant microspheres are stirred evenly to obtain a mixture; (3) The mixture is fed into a twin-screw extruder to side-feed the modified carbon fiber, and then extruded and granulated to obtain a high-performance composite material.

[0039] In this comparative example, the coated carbon fiber from Example 2 and the flame-retardant microspheres for preventing exudation from Example 4 were used.

[0040] Performance testing Samples were prepared using the high-performance composite materials from Examples 5-7 and Comparative Examples 1-3. The sample from Example 6 was stored at 85°C / 85% humidity for 192 hours and was designated as aging sample A. The sample from Comparative Example 1 was stored at 85°C / 85% humidity for 192 hours and was designated as aging sample B. The samples were then tested.

[0041] 1. Ablation Performance Test: The ablation performance of the samples was tested using an oxygen-acetylene ablation test, according to the standard GJB 323A-2019. The test conditions were adjusted to 500 L / h oxygen and 560 L / h acetylene, with a heat flux density of approximately 1800 kW / m³. 2 The sample was adjusted to a cylinder with a diameter of 30 mm and a thickness of 10 mm, and placed in a graphite mold for ablation testing. The distance between the sample and the flame nozzle was 50 mm, and the ablation time was 40 s. The linear ablation rate and mass ablation rate were calculated using the following formulas: In the formula: Linear ablation rate, mm / s; The mass ablation rate is expressed in g / s. The thickness of the sample before ablation is in mm; The thickness of the sample before ablation is in mm; The mass of the sample before ablation is in grams. The mass of the sample after ablation is in grams. The ablation time is in seconds (s).

[0042] The specific test results are shown in Table 1.

[0043] Table 1. Resistance to ablation As shown in Table 1, compared with Example 6, the carbon fiber used in Comparative Example 2 was not coated with zirconium oxide film, and its ablation resistance was reduced; the carbon nanotubes were not added to the sample in Comparative Example 3, and its ablation resistance was also reduced; compared with the aged sample A, the ablation resistance of the aged sample B was significantly reduced, indicating that the agglomeration and precipitation problems caused by directly adding ammonium polyphosphate flame retardant seriously affected the ablation resistance.

[0044] 2. Friction Resistance Test: The samples were tested using a friction and wear testing machine. The friction load was controlled at 15 N, and the wear time was 30 min. The wear volume was used to characterize the friction resistance. The specific test results are shown in Table 2.

[0045] Table 2 Abrasion Resistance As shown in Table 2, compared with Example 6, the sample in Comparative Example 2 used carbon fiber without zirconium oxide film, and the sample in Comparative Example 3 did not add carbon nanotubes. The abrasion resistance of both was reduced.

[0046] Combination Figure 1 It can be seen that the surface of aged sample A is relatively smooth with almost no precipitates, while the surface of aged sample B has significantly more precipitates.

[0047] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A high performance composite material, characterized in that, The raw materials include the following parts by weight: 120-150 parts of polyphenylene ether resin, 1-3 parts of antioxidant, 10-15 parts of coated carbon fiber, 15-20 parts of anti-precipitation flame-retardant microspheres, and 5-10 parts of carbon nanotubes. The preparation method of the coated carbon fiber is as follows: S11, dissolve zirconium acetylacetonate in N,N-dimethylformamide, heat and stir until clear and transparent to obtain a zirconium oxide precursor solution; S12, ultrasonically disperse carbon fiber in the zirconium oxide precursor solution, stir continuously and then separate, and treat with ultraviolet light to form a zirconium oxide film on the surface of the carbon fiber, thus obtaining the coated carbon fiber. The preparation method of the anti-precipitation flame-retardant microspheres is as follows: S21, dissolve ammonium polyphosphate in deionized water to obtain a flame-retardant solution; S22, immerse porous polystyrene microspheres in the flame-retardant solution, treat with pressure and then separate, and then dry, repeat the immersion and drying process more than 3 times to obtain the anti-precipitation flame-retardant microspheres.

2. The high performance composite of claim 1, wherein, The antioxidant is selected from antioxidant 1010, antioxidant DLTP and antioxidant 168.

3. The high performance composite of claim 1, wherein, In step S11, the heating and stirring temperature is 90-95℃; the mass ratio of zirconium acetylacetonate to N,N-dimethylformamide is 1:(10-12).

4. The high-performance composite material according to claim 2, characterized in that, In step S12, the continuous stirring time is 1.5-2 hours; the ultraviolet irradiation treatment time is 1.2-1.5 hours.

5. The high-performance composite material according to claim 4, characterized in that, In step S21, the ratio of ammonium polyphosphate to deionized water is 1:(5-8)g / mL.

6. The high-performance composite material according to claim 4, characterized in that, In step S22, the pressurization process involves maintaining pressure at 1-1.5 MPa for 2-3 hours.

7. The method for preparing the high-performance composite material according to any one of claims 1-6, characterized in that, Includes the following steps: (1) Silane coupling agent was used to modify the surface of coated carbon fibers and carbon nanotubes respectively to obtain modified carbon fibers and modified carbon nanotubes. (2) The polyphenylene ether resin, antioxidant, flame-retardant microspheres and modified carbon nanotubes are stirred evenly to obtain a mixture; (3) The mixture is fed into a twin-screw extruder to side-feed the modified carbon fiber, and then extruded and granulated to obtain a high-performance composite material.

8. The method for preparing high-performance composite materials according to claim 7, characterized in that, In step (1), the silane coupling agent is selected from KH-550 and KH-560.

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