石墨烯纳米片改性高模碳纤维复合材料的界面及湿热性能

毛新东; 田艳红; 孙江曼; 张学军

石墨烯纳米片改性高模碳纤维复合材料的界面及湿热性能

北京化工大学　碳纤维及功能高分子教育部重点实验室, 北京 100029

详细信息

通讯作者:
张学军，博士，研究员，硕士生导师，研究方向为高模量碳纤维及其复合材料界面性能　E-mail：zhangxj@mail.buct.edu.cn

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- 被引次数: 0
出版历程
- 收稿日期: 2024-05-13
- 修回日期: 2024-06-21
- 录用日期: 2025-01-14
- 网络出版日期: 2024-07-18

Interfacial and hygrothermal properties of high modulus carbon fiber composites modified with graphene nanoplates

Key Laboratory of Carbon Fiber and Functional Polymers of Ministry of Education, Beijing University of Chemical Technology, Beijing 100029, China

摘要

摘要: 高模量碳纤维(HMCF)复合材料的界面性能一直是影响其应用的关键所在，对HMCF进行表面改性则是实现界面性能提高的重要途径之一。采用电泳沉积法将石墨烯纳米片(GNP)引入到HMCF表面，通过扫描电镜(SEM)、X射线光电子能谱(XPS)对改性前后的HMCF表面形貌、表面化学状态进行了表征，测试了改性前后HMCF增强环氧树脂复合材料的层间剪切强度(ILSS)和吸湿率。结果表明，HMCF表面电泳沉积GNP，不仅可以改善其增强环氧树脂复合材料的界面性能，同时也能降低复合材料的吸湿率。在GNP浓度为0.5 mg/mL，电泳沉积电压为10 V时，复合材料层间剪切性能提高了8.8%，达到75.6 MPa；90℃、80RH%环境下存放30天后，与未改性样品相比，其吸湿率降低了9.5%，存放60天后层间剪切性能仍保持在67.8 MPa。改性高模量碳纤维复合材料界面性能与耐湿热性能均得以提高。
- 高模碳纤维 /
- GNP /
- 电泳沉积 /
- 复合材料 /
- 湿热性能 /
- 界面性能
Abstract: The interfacial properties of high-modulus carbon fiber (HMCF) composites have always been the key to their applications, and surface modification of HMCF is one of the important ways to improve the interfacial properties. Graphene nanosheets (GNP) were introduced into the surface of HMCF by electrophoretic deposition, and the surface morphology and surface chemical state of HMCF before and after modification were characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), and the interlaminar shear strength (ILSS) and moisture absorption rate of HMCF reinforced epoxy resin composites before and after modification were tested. The results show that the surface electrophoretic deposition of GNP by HMCF can not only improve the interfacial properties of the reinforced epoxy resin composites, but also reduce the moisture absorption rate of the composites. When the GNP concentration was 0.5 mg/mL and the electrophoretic deposition voltage was 10 V, the interlaminar shear performance of the composites increased by 8.8% to 75.6 MPa, and the moisture absorption rate was reduced by 9.5% compared with the unmodified sample after 30 days of storage at 90°C and 80 RH%, and the interlayer shear performance remained at 67.8 MPa after 60 days of storage. Both interfacial and hygrothermal properties of the modified HMCF comosites have been improved.
- high modulus carbon fiber /
- graphene nanoplates /
- electrophoresis deposition /
- composite /
- hygrothermal properties /
- interfacial properties.

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图 1 U-CF(a)、CF-5(b)、CF-10(c)、CF-20(d)的SEM图像

Figure 1. SEM images of U-CF(a)、CF-5(b)、CF-10(c)、CF-20(d)；

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图 2 HMCF的XPS广谱图；C1 s的分峰拟合图谱(a)U-CF(b)CF-5(c)CF-10(d)CF-20

Figure 2. XPS broad spectrum of HMCF(a) C1 s peak fitting diagrams of (a) U-CF (b) CF-5 (c) CF-10 (d) CF-20

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图 3 不同HMCF/EP复合材料的层间剪切强度

Figure 3. Interlaminar shear strength of different HMCF/EP composites

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图 4 不同HMCF/EP复合材料横断面SEM图像：(a) U-CF/EP; (b) CF-5/EP; (c) CF-10/EP; (d) CF-20/EP

Figure 4. Cross-sectional SEM images of different HMCF/EP composites: (a) U-CF/EP; (b) CF-5/EP; (c) CF-10/EP; (d) CF-20/EP

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图 5 90℃、80 RH%下HMCF/EP吸湿率随时间的Fick二段扩散模型拟合

Figure 5. Fitting of the Fick two-stage diffusion model of HMCF/EP moisture absorption over time at 90°C, 80 RH%

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图 6 CF-10/EP经不同湿热时间下复合材料的纵断面(a) 0d; (b) 10d;(c) 20d; (d) 30d

Figure 6. Profile of CF-10/EP under different hygrothermal times (a) 0d;(b) 10d; (c) 20d; (d) 30d

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图 7 不同HMCF/EP复合材料轴向截面形态SEM图像(a) U-CF/EP; (a1) Aged U-CF/EP; (b) CF-10/EP; (b1) Aged CF-10/EP; (c) CF-20/EP; (c1) Aged CF-20/EP

Figure 7. SEM images of axial cross-section morphology of different HMCF/EP composites (a) U-CF/EP; (a1)Aged U-CF/EP; (b) CF-10/EP; (b1) Aged CF-10/EP; (c) CF-20/EP; (c1) Aged CF-20/EP

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图 8 不同HMCF/EP复合材料经湿热试验后的界面失效机制(a) U-CF/EP; (b) CF-10/EP; (c) CF-20/EP

Figure 8. Interfacial failure mechanisms of different HMCF/EP composites after hygrothermal test (a) U-CF/EP; (b) CF-10/EP; (c) CF-20/EP

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表 1 各样品缩写命名

Table 1. Abbreviations used for various samples prepared

Sample code	Details
U-CF	Untreated commercial carbon fibers (CF)
CF	0.5 mg/mL solution 5 V voltage electrophoresis deposited modified fibers
CF-10	0.5 mg/mL graphene nanoplates solution 10 V voltage electrophoresis deposited modified fibers
CF-20	0.5 mg/mL graphene nanoplates solution 20 V voltage electrophoresis deposited modified fibers
U-CF/EP	Untreated commercial carbon fiber reinforced epoxy (EP) composites
CF-5/EP	0.5 mg/mL graphene nanoplates solution 5 V voltage electrophoresis deposited modified fibers reinforced epoxy composites
CF-10/EP	0.5 mg/mL graphene nanoplates solution 10 V voltage electrophoresis deposited modified fibers reinforced epoxy composites
CF-20/EP	0.5 mg/mL graphene nanoplates solution 20 V voltage electrophoresis deposited modified fibers reinforced epoxy composites
Aged U-CF/EP	After 30 days of hygrothermal test(90℃、80%RH) untreated commercial carbon fibers reinforced epoxy composites
Aged CF-5/EP	After 30 days of hygrothermal test(90℃、80%RH) 0.5 mg/mL graphene nanoplates solution 5 V voltage electrophoresis deposited modified fibers reinforced epoxy composites
Aged CF-10/EP	After 30 days of hygrothermal test(90℃、80%RH) 0.5 mg/mL graphene nanoplates solution 10 V voltage electrophoresis deposited modified fibers reinforced epoxy composites
Aged CF-20/EP	After 30 days of hygrothermal test(90℃、80%RH) 0.5 mg/mL graphene nanoplates solution 20 V voltage electrophoresis deposited modified fibers reinforced epoxy composites

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表 2 不同HMCF C1 s特征峰结合能及相对含量

Table 2. C1 s characteristic peak binding energy and relative content of different HMCF

Functional group	Binding energy/eV	U-CF/%	CF-5/%	CF-10/%	CF-20/%
C—C	284.4	46.60	48.31	49.36	44.56
C—H	285.2	48.78	46.08	46.59	45.76
C—O	286.3	2.19	2.69	1.35	4.65
C=O	287.3	/	/	/	/
COOH	288.6	0.72	1.70	3.79	3.78

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表 3 90℃、80 RH%湿热条件下HMCF/EP的吸湿率

Table 3. Moisture absorption of HMCF/EP at 90°C, 80 RH%

Sample	M_{5 d}/%	M_{10 d}/%	M_{15 d}/%	M_{20 d}/%	M_{25 d}/%	M_{30 d}/%
U-CF	0.08	0.16	0.21	0.24	0.25	0.26
CF-10/EP	0.07	0.15	0.19	0.21	0.22	0.24
CF-20/EP	0.08	0.17	0.22	0.22	0.24	0.25
Note：M_xd—Moisture absorption of composite material after x days

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表 4 80 RH%，90℃湿热老化HMCF/EP吸湿拟合参数

Table 4. Hygroscopic fitting parameters of HMCF/EP for hygrothermal at 90°C，80 RH%

	CF-10/EP	CF-20/EP	U-CF/EP
D/10⁻⁴mm/h	14.82	15.13	15.69
M_1∞/%	0.12	0.14	0.12
M_{30 d}/%	0.24	0.25	0.26
k/10⁻² mm/h^1/2	4.43	3.89	5.19
R²	0.96	0.95	0.97
Note：D—Diffusion coefficient of water molecules in composites M_1∞—Saturated moisture absorption rate of the first stage of the composite Fick M_{30 d}—Moisture absorption of composite material after 30 days k—Constant related to the relaxation of resin structure

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表 5 80 RH%、90℃下HMCF/EP老化过程中层间剪切强度

Table 5. Interlaminar shear strength during HMCF/EP aging at 90℃、80 RH%

Sample	ILSS_0d/MPa	ILSS_10d/MPa	ILSS_20d/MPa	ILSS_30d/MPa	ILSS_60d/MPa
U-CF/EP	69.5	68.6	65.4	64.4	61.3
CF-10/EP	75.6	73.2	69.3	69.5	67.8
CF-20/EP	72.2	68.9	68.1	66.7	65.5
Note：ILSS_xd—Interlaminar shear strength of composite material after x days

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