A modified carbon fiber-reinforced phenolic resin composite material and a method for manufacturing the same

Abstract

The application discloses a modified carbon fiber reinforced phenolic resin composite material and a preparation method thereof, relates to the technical field of wear-resistant materials, and solves the problem that the existing carbon fiber is difficult to improve the wear resistance of a phenolic resin. The method comprises the following steps: performing steady flow electroplating of an oxidized graphene coating on a carbon fiber cloth in an oxidized graphene / potassium hydroxide suspension, and performing cleaning and drying; immersing the treated carbon fiber cloth in an ammonium molybdate / thiourea aqueous solution, and placing the carbon fiber cloth in a hydrothermal reaction kettle to perform hydrothermal reaction; performing cleaning and drying on the carbon fiber cloth after the hydrothermal reaction, so as to obtain a carbon fiber cloth on which vertical sheet-shaped molybdenum disulfide and horizontal layered graphene are grown and modified; and immersing the carbon fiber cloth in a phenolic resin, and then performing hot pressing to obtain the modified carbon fiber reinforced phenolic resin composite material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of wear-resistant materials, and particularly relates to a modified carbon fiber reinforced phenolic resin composite material and a preparation method thereof. BACKGROUND

[0002] Phenolic resin has the advantages of high temperature resistance, good acid resistance, strong wear resistance, good mechanical and electrical properties, non-degradability, long storage time and the like, and is a good resin matrix material. At present, a large amount of work at home and abroad is focused on introducing a reinforcing body into the phenolic resin to further enhance the mechanical properties, wear resistance and flame retardant properties of the phenolic resin.

[0003] As a fiber reinforcing body, carbon fiber can be used to synthesize a composite material with resin, ceramic, metal, cement, carbon or rubber as a matrix, and has high specific strength and specific rigidity in many lightweight materials, and the lightweight effect is very obvious. However, as a reinforcing body of phenolic resin, carbon fiber can only enhance the mechanical strength of phenolic resin, and has limited improvement on wear resistance. SUMMARY

[0004] In order to solve the problem of difficulty in improving the wear resistance of phenolic resin by using carbon fiber, the present application provides a modified carbon fiber reinforced phenolic resin composite material and a preparation method thereof.

[0005] The technical scheme of the present application is as follows:

[0006] A preparation method of a modified carbon fiber reinforced phenolic resin composite material, comprising the following steps:

[0007] S1, electroplating an oxidized graphene coating on a carbon fiber cloth in an oxidized graphene / potassium hydroxide suspension, and cleaning and drying;

[0008] S2, soaking the treated carbon fiber cloth in an ammonium molybdate / thiourea aqueous solution, and placing it in a hydrothermal reaction kettle for hydrothermal reaction;

[0009] S3, cleaning and drying the carbon fiber cloth after hydrothermal reaction to obtain a carbon fiber cloth modified with vertically sheet-shaped molybdenum disulfide@horizontally layered graphene;

[0010] S4, immersing the carbon fiber cloth of step S3 in phenolic resin, and then hot pressing to obtain a modified carbon fiber reinforced phenolic resin composite material.

[0011] Preferably, the concentration of oxidized graphene in the oxidized graphene / potassium hydroxide suspension is 0.8g / L-1.5g / L.

[0012] Preferably, the pH of the oxidized graphene / potassium hydroxide suspension in step S1 is 11-12.

[0013] Preferably, the constant-current plating time of the constant-current plating in step S1 is 8 min to 20 min.

[0014] Preferably, the constant-current plating voltage of the constant-current plating in step S1 is 0.5 A to 2.5 A.

[0015] Preferably, the electrode area ratio of the constant-current plating in step S1 is that the area of the carbon fiber cloth is not more than twice the area of the contrast electrode.

[0016] Preferably, the concentration of ammonium molybdate in the ammonium molybdate / thiourea aqueous solution in step S2 is 10 g / L to 40 g / L, the concentration of thiourea is 30 g / L to 100 g / L, and the molar ratio of ammonium molybdate to thiourea is 1:30 to 1:40.

[0017] Preferably, the reaction temperature of the hydrothermal reaction in step S2 is 180°C to 200°C.

[0018] Preferably, the reaction time of the hydrothermal reaction in step S2 is 5 h to 10 h.

[0019] A modified carbon fiber reinforced phenolic resin composite material is prepared by the preparation method.

[0020] Compared with the prior art, the present application solves the problem of difficulty in improving the wear resistance of carbon fiber to phenolic resin, and has the following specific beneficial effects:

[0021] The method provided by the present application is simple in process, easy to implement, low in cost, and small in environmental pollution, and overcomes the problem of insufficient wear resistance of the existing carbon fiber reinforced phenolic resin. The friction coefficient of the modified carbon fiber reinforced phenolic resin composite material prepared by modifying the carbon fiber is far less than that of the untreated carbon fiber reinforced phenolic resin, greatly improving the wear resistance and having a good application prospect in the field of wear-resistant materials. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 It is a scanning electron microscope graph of the graphene oxide treated carbon fiber cloth in Example 1.

[0023] Figure 2 It is a scanning electron microscope graph of the molybdenum disulfide@graphene oxide treated carbon fiber cloth in Example 1.

[0024] Figure 3 It is an EDS energy spectrum graph of the modified carbon fiber reinforced phenolic resin composite material in Example 1.

[0025] Figure 4 It is an infrared spectrum diffraction comparison graph of the modified carbon fiber reinforced phenolic resin composite material and the unmodified carbon fiber reinforced phenolic resin composite material in Example 1.

[0026] Figure 5 Figure 1 is a comparison chart of XRD diffraction of the modified carbon fiber reinforced phenolic resin composite material and the unmodified carbon fiber reinforced phenolic resin composite material in Example 1.

[0027] Figure 6 Figure 2 is a comparison chart of friction coefficient of the modified carbon fiber reinforced phenolic resin composite material and the unmodified carbon fiber reinforced phenolic resin composite material in Example 1. DETAILED DESCRIPTION

[0028] In order to make the technical solutions of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the drawings of the specification of the present application. It should be noted that the following embodiments are only used to better understand the technical solutions of the present application, and should not be understood as a limitation on the present application.

[0029] Example 1.

[0030] The carbon fiber cloth was cut into a size of 10 cm x 10 cm and soaked in acetone for 48 h to remove the surface sizing;

[0031] 1 g of graphene oxide was added to 1 L of deionized water, stirred uniformly, mixed thoroughly, and then ultrasonically treated for 2 h. 1 mol / L potassium hydroxide solution was added dropwise to the suspension until the pH of the suspension was 11, and then ultrasonically treated for another 2 h.

[0032] The carbon fiber cloth was used as the positive electrode, an 8.5 cm x 8.5 cm graphite electrode plate was used as the negative electrode, and the suspension obtained by ultrasonic treatment was used as the electroplating solution. The current was controlled to be stable at 1 A, and electroplating was carried out for 8 min. The carbon fiber cloth obtained after electroplating treatment was washed and dried to obtain graphene oxide treated carbon fiber cloth. The graphene oxide treated carbon fiber cloth was observed by scanning electron microscopy, as shown in Figure 1 The rough and wrinkled surface in the figure indicates that a thin layer of graphene oxide has been deposited on the surface of the carbon fiber, and as can be seen from the figure, the graphene oxide can be very uniformly laid on the surface of the carbon fiber after the electrodeposition step.

[0033] Ammonium molybdate 2 g, thiourea 5 g, were dissolved in 80 mL of deionized water, mixed uniformly, and then placed in the inner liner of a polytetrafluoroethylene autoclave. The graphene oxide treated carbon fiber cloth was also placed in the inner liner of the autoclave, and the autoclave was assembled. The reaction time was controlled to be 8 h, and the reaction temperature was controlled to be 200℃.

[0034] The autoclave was opened after the reaction was completed, and the molybdenum disulfide@graphene oxide treated carbon fiber cloth was obtained after washing and drying. The molybdenum disulfide@graphene oxide treated carbon fiber cloth was observed by scanning electron microscopy, as shown in Figure 2As shown, the molybdenum disulfide is uniformly and densely distributed on the surface of the carbon fiber, without obvious agglomeration, and most of the molybdenum disulfide is attached to the surface of the carbon fiber in a vertical state.

[0035] The molybdenum disulfide@graphene oxide treated carbon fiber cloth is mixed with 20 g of phenolic resin, and placed in a hot press, with the hot pressing temperature controlled at 150°C, and the hot pressing time controlled at 20 min, to obtain a modified carbon fiber reinforced phenolic resin composite material.

[0036] Figure 3 The EDS spectrum of the modified carbon fiber reinforced phenolic resin composite material prepared in this example shows that the carbon fiber is the main material, and should contain a large amount of carbon element detected by the element. However, because the surface of the carbon fiber is distributed with uniformly and densely combined graphene oxide@molybdenum disulfide structure, the carbon element is rarely detected on the surface of the carbon fiber, and the C element EDS spectrum shows obvious voids. The EDS spectrum of Mo element and S element shows that Mo element and S element are very uniformly distributed in the center of the EDS spectrum, and the element distribution angle shows that the molybdenum disulfide is generated on the surface of the carbon fiber and uniformly distributed. Figure 4 The infrared spectrum diffraction comparison chart of the modified carbon fiber reinforced phenolic resin composite material prepared in this example and the unmodified carbon fiber reinforced phenolic resin composite material is shown in the figure. As shown, in the case of molybdenum disulfide attached to the surface of the carbon fiber, a relatively obvious diffraction peak appears at 563 cm -1 , corresponding to the existence of Mo-S, and the C=C stretching vibration peak appearing at 1660 cm -1 has a 20 cm -1 shift, which may be due to the influence of the existence of molybdenum disulfide on the diffraction peak. Figure 5 The XRD diffraction comparison chart of the modified carbon fiber reinforced phenolic resin composite material prepared in this example and the unmodified carbon fiber reinforced phenolic resin composite material shows that the diffraction peak of the carbon fiber is the most obvious, occupying the vast majority of the spectrum position, but in addition to the carbon fiber diffraction peak occupying the vast position, relatively weak diffraction peaks appear at 2θ = 14.51°, 32.34°, respectively, corresponding to the (0 02) and (1 0 1) planes of molybdenum disulfide. Figure 6The friction coefficient comparison chart of the modified carbon fiber reinforced phenolic resin composite material prepared in this embodiment and the unmodified carbon fiber reinforced phenolic resin composite material can show that the friction coefficient of the modified carbon fiber reinforced phenolic resin composite material prepared in this embodiment is obviously lower than that of the unmodified carbon fiber reinforced phenolic resin composite material. It is calculated that the average friction coefficient of the composite material prepared in this embodiment is about 0.28, which is less than the average value of the unmodified carbon fiber reinforced phenolic resin with an average friction coefficient of about 0.5, that is, the friction coefficient is effectively reduced, and the wear resistance is greatly improved.

[0037] In this embodiment, graphene oxide is used as a friction material reinforcing body. It can not only slide between layers to enhance the wear resistance of the material, but also form a heat conduction network by using its strong heat conductivity to relieve the thermal damage of the material caused by high temperature generated during friction. In addition, there are many active sites on the surface of graphene oxide, which can be modified on its surface to further enhance the strength of the system. Molybdenum disulfide further combines with graphene to form a heterostructure, which further improves the tribological properties of carbon fiber and has good application prospect in the field of wear-resistant materials.

[0038] Embodiment 2.

[0039] The carbon fiber cloth is cut into a size of 10 cm x 9 cm and soaked in acetone for 48 h to remove the surface sizing;

[0040] 0.8 g of graphene oxide is added to 1 L of deionized water, stirred uniformly, mixed thoroughly, and then ultrasonically treated for 2 h. 1 mol / L potassium hydroxide solution is added dropwise until the pH of the suspension is 12, and then ultrasonic treatment is performed for another 2 h;

[0041] The carbon fiber cloth is used as the positive electrode, the 8x8 cm graphite electrode plate is used as the negative electrode, and the suspension obtained by ultrasonic treatment is used as the electroplating solution. The current is controlled to be stable at 1.5 A, and the electroplating process is carried out for 10 min. The carbon fiber cloth obtained after electroplating treatment is washed and dried to obtain the graphene oxide treated carbon fiber cloth;

[0042] 1.3 g of ammonium molybdate and 3.5 g of thiourea are dissolved in 80 mL of deionized water, mixed uniformly, and then placed in a polytetrafluoroethylene autoclave liner. The graphene oxide treated carbon fiber cloth is also placed in the autoclave liner, and the autoclave is assembled. The reaction time is controlled to be 10 h, and the reaction temperature is controlled to be 220°C.

[0043] The autoclave is opened after the reaction is completed, and the molybdenum disulfide@graphene oxide treated carbon fiber cloth is taken out, washed and dried, and then mixed with 20 g of phenolic resin. The mixture is placed in a hot press, the hot pressing temperature is controlled to be 120°C, and the hot pressing time is controlled to be 20 min. A modified carbon fiber reinforced phenolic resin composite material is obtained.

[0044] The modified carbon fiber reinforced phenolic resin composite prepared in the embodiment has a friction coefficient significantly lower than that of the untreated carbon fiber reinforced phenolic resin composite. The average friction coefficient of the composite prepared in the embodiment is about 0.3, which is less than the average value of the untreated carbon fiber reinforced phenolic resin with an average friction coefficient of about 0.5. That is, the friction coefficient is effectively reduced, and the wear resistance is greatly improved.

Claims

1. A method for preparing a modified carbon fiber reinforced phenolic resin composite material, characterized in that: The following steps are involved: S1. Electroplating a graphene oxide coating on a carbon fiber cloth in a graphene oxide / potassium hydroxide suspension at a steady flow rate, followed by washing and drying. S2, soaking the treated carbon fiber cloth in an ammonium molybdate / thiourea aqueous solution and placing the cloth in a hydrothermal reactor for a hydrothermal reaction; S3, washing and drying the carbon fiber cloth after the hydrothermal reaction to obtain a carbon fiber cloth modified with vertical flaky molybdenum disulfide and horizontal layered graphene; S4, immersing the carbon fiber cloth obtained in step S3 in phenolic resin, and then hot-pressing the cloth to obtain a modified carbon fiber reinforced phenolic resin composite material.

2. The method for preparing a modified carbon fiber reinforced phenolic resin composite material according to claim 1, wherein: The graphene oxide concentration in the graphene oxide / potassium hydroxide suspension is 0.8 g / L to 1.5 g / L.

3. The method for preparing a modified carbon fiber reinforced phenolic resin composite material according to claim 1, wherein: The pH of the graphene oxide / potassium hydroxide suspension in step S1 is 11-12.

4. The method for preparing a modified carbon fiber reinforced phenolic resin composite material according to claim 1, wherein: The steady-current electroplating time of the steady-current electroplating in step S1 is 8 minutes to 20 minutes.

5. The method for preparing a modified carbon fiber reinforced phenolic resin composite material according to claim 1, wherein: The steady current voltage of the steady current electroplating in step S1 is 0.5A to 2.5A.

6. The method for preparing a modified carbon fiber reinforced phenolic resin composite material according to claim 1, wherein: The area of ​​the carbon fiber cloth subjected to steady-current electroplating in step S1 is no more than twice the area of ​​the comparison electrode.

7. The method for preparing a modified carbon fiber reinforced phenolic resin composite material according to claim 1, wherein: In step S2, the concentration of ammonium molybdate in the ammonium molybdate / thiourea aqueous solution is 10 g / L to 40 g / L, the concentration of thiourea is 30 g / L to 100 g / L, and the molar ratio of ammonium molybdate to thiourea is 1:30 to 1:

40.

8. The method for preparing a modified carbon fiber reinforced phenolic resin composite material according to claim 1, wherein: The reaction temperature of the hydrothermal reaction in step S2 is 180°C to 200°C.

9. The method for preparing a modified carbon fiber reinforced phenolic resin composite material according to claim 1, wherein: The reaction time of the hydrothermal reaction in step S2 is 5 h to 10 h.

10. A modified carbon fiber reinforced phenolic resin composite material, characterized in that: The composite material is prepared by the preparation method according to any one of claims 1 to 9.

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