Ti3C2Tx-MXene上浆剂表面改性高模量碳纤维及其环氧树脂基复合材料界面性能

董玉双; 张学军; 田艳红; 黄玲

doi:10.13801/j.cnki.fhclxb.20210918.001

Ti₃C₂T_x-MXene上浆剂表面改性高模量碳纤维及其环氧树脂基复合材料界面性能

doi: 10.13801/j.cnki.fhclxb.20210918.001

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　 E-mail：zhangxj@mail.buct.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2021-07-29
- 修回日期: 2021-08-25
- 录用日期: 2021-08-31
- 网络出版日期: 2021-09-22
- 刊出日期: 2022-08-31

Ti₃C₂T_x-MXene sizing agent surface modified high modulus carbon fiber and its epoxy resin matrix composites interface properties

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

摘要

摘要: 为了改善高模量碳纤维(HMCF)表面润湿性及增强其复合材料界面性能，本文采用机械共混法，将尺寸为100~500 nm的少层Ti₃C₂T_x-MXene水分散液与水性环氧乳液上浆剂进行复配，制备了适用于HMCF的Ti₃C₂T_x-MXene/环氧树脂(EP)改性环氧乳液复合上浆剂，并以连续上浆技术在HMCF表面构筑了富含Ti₃C₂T_x-MXene的特性涂层，以期改善HMCF/EP复合材料的界面结合性能。通过SEM、XPS和动态接触角测试对HMCF的表面形貌、表面化学状态和表面润湿性能进行了表征，并以层间剪切强度(ILSS)和断面形貌测试对HMCF/EP复合材料的界面结合状况进行了分析表征，最后以复合材料的剪切破坏模型对Ti₃C₂T_x-MXene/EP复合上浆剂改性的HMCF/EP复合材料的界面增强机制进行了探讨。结果表明，经Ti₃C₂T_x-MXene/EP复合上浆剂表面处理后，HMCF表面的O/C(原子比)提高，并赋予其一定量的纳米尺度小凸起微机械结构，改善了HMCF的表面润湿性。当环氧乳液上浆剂固含量为0.8%，Ti₃C₂T_x-MXene浓度为1.0 mg/mL时，HMCF/EP复合材料的ILSS值提高了23.8%，达到85.9 MPa。
- 高模量碳纤维 /
- Ti₃C₂T_x-MXene /
- 上浆剂 /
- 复合材料 /
- 界面性能
Abstract: In order to improve the surface wettability of high modulus carbon fibers (HMCF) and enhance the interfacial properties of their composites, a few-layer Ti₃C₂T_x-MXene aqueous dispersion with a size of 100-500 nm was mixed with an aqueous epoxy emulsion to prepare an Ti₃C₂T_x-MXene modified sizing agent for HMCF by mechanical blending method. The continuous sizing technology was used to construct a characteristic coating rich in Ti₃C₂T_x-MXene on the surface of HMCF in order to improve the interface bonding of HMCF/epoxy resin (EP) composites. The surface morphology, surface chemical state and surface wettability of HMCF were characterized by SEM, XPS and dynamic contact angle test, and the interface bonding of HMCF/EP composites was analyzed and characterized by interlaminar shear strength (ILSS) and cross-sectional morphology tests. Finally, the interface enhancement mechanism of Ti₃C₂T_x-Mxene/EP sizing agent-modified HMCF/EP composites was investigated with the shear damage models of the composites. The results show that after the surface treatment with Ti₃C₂T_x-MXene modified sizing agent, the O/C (atomic ratio) of the HMCF surface is increased, and a certain amount of nano-scale convex micromechanical structures are introduced to improve the surface wettability of HMCF. When the solid content of the epoxy emulsion sizing agent is 0.8% and the concentration of Ti₃C₂T_x-MXene is 1.0 mg/mL, the ILSS of the HMCF/EP composites increases by 23.8% to 85.9 MPa.
- high modulus carbon fiber /
- Ti₃C₂T_x-MXene /
- sizing agent /
- composite /
- interfacial properties

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图 1 BHM2型高模量碳纤维(HMCF)上浆装置图

Figure 1. Sizing device diagram of BHM2 type high modulus carbon fibers (HMCF)

MXene-SCF—Ti₃C₂T_x-MXene sized carbon fibers

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图 2 Ti₃AlC₂-MAX (a)、多层Ti₃C₂T_x-MXene (b) 的SEM图像，少层Ti₃C₂T_x-MXene的TEM图像 (c) 和Ti₃C₂T_x-MXene/环氧树脂(EP)复合上浆剂外观图 (d)

Figure 2. SEM image of Ti₃AlC₂-MAX (a), multi-layer Ti₃C₂T_x-MXene (b), TEM image of few-layer Ti₃C₂T_x-MXene (c) and appearance of Ti₃C₂T_x-MXene/epoxy resin (EP) composite sizing agent (d)

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图 3 Ti₃C₂T_x-MXene的C1s (a) 和O1s (b) XPS分峰拟合图

Figure 3. C1s (a) and O1s (b) XPS peak fitting diagram of Ti₃C₂T_x-MXene

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图 4 D-HMCF (a)、Ti₃C₂T_x-0MXene-SCF (b)、Ti₃C₂T_x-0.5MXene-SCF (c)、Ti₃C₂T_x-1.0MXene-SCF (d)、Ti₃C₂T_x-1.5MXene-SCF (e) 和Ti₃C₂T_x-2.0MXene-SCF (f) 的SEM图像

Figure 4. SEM images of D-HMCF (a), Ti₃C₂T_x-0MXene-SCF (b), Ti₃C₂T_x-0.5MXene-SCF (c), Ti₃C₂T_x-1.0MXene-SCF (d), Ti₃C₂T_x-1.5MXene-SCF (e) and Ti₃C₂T_x-2.0MXene-SCF (f)

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图 5 不同HMCF的XPS广谱图 (a)、D-HMCF (b)、Ti₃C₂T_x-0MXene-SCF (c) 和Ti₃C₂T_x-1.0MXene-SCF (d) 的C1s分峰拟合图谱

Figure 5. XPS broad spectrum of different HMCF (a), C1s peak fitting diagrams of D-HMCF (b), Ti₃C₂T_x-0MXene-SCF (c) and Ti₃C₂T_x-1.0MXene-SCF (d)

O/C—Atomic ratio of O/C

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图 6 不同处理HMCF的接触角 (a) 及表面能 (b)

Figure 6. Contact angle (a) and surface energy (b) of different HMCF

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图 7 不同HMCF/EP复合材料的层间剪切强度

Figure 7. Interlaminar shear strength of different HMCF/EP composites

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图 8 D-HMCF/EP (a)、Ti₃C₂T_x-0MXene-SCF/EP (b)、Ti₃C₂T_x-0.5MXene-SCF/EP (c)、Ti₃C₂T_x-1.0MXene-SCF/EP (d)、Ti₃C₂T_x-1.5MXene-SCF/EP (e) 和Ti₃C₂T_x-2.0MXene-SCF/EP (f) 的断面形貌

Figure 8. Cross-sectional morphologies of D-HMCF/EP (a), Ti₃C₂T_x-0MXene-SCF/EP (b), Ti₃C₂T_x-0.5MXene-SCF/EP (c), Ti₃C₂T_x-1.0MXene-SCF/EP (d), Ti₃C₂T_x-1.5MXene-SCF/EP (e) and Ti₃C₂T_x-2.0MXene-SCF/EP (f)

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图 9 D-HMCF/EP (a)、Ti₃C₂T_x-0MXene-SCF/EP (b) 和Ti₃C₂T_x-1.0MXene-SCF/EP (c) 的界面破坏机制图

Figure 9. Diagram of the interface destruction mechanism of D-HMCF/EP (a), Ti₃C₂T_x-0MXene-SCF/EP (b) and Ti₃C₂T_x-1.0MXene-SCF/EP (c)

CF—Carbon fibers

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表 1 各样品缩写命名

Table 1. Abbreviations used for various samples prepared

Sample code		Details
D-HMCF		Desized BHM2 carbon fibers
U-HMCF		BHM2 carbon fibers
Ti₃C₂T_x-0MXene-SCF		0 mg/mL Ti₃C₂T_x-MXene/EP composite sizing agent sized carbon fibers
Ti₃C₂T_x-0.5MXene-SCF		0.5 mg/mL Ti₃C₂T_x-MXene/EP composite sizing agent sized carbon fibers
Ti₃C₂T_x-1.0MXene-SCF		1.0 mg/mL Ti₃C₂T_x-MXene/EP composite sizing agent sized carbon fibers
Ti₃C₂T_x-1.5MXene-SCF		1.5 mg/mL Ti₃C₂T_x-MXene/EP composite sizing agent sized carbon fibers
Ti₃C₂T_x-2.0MXene-SCF		2.0 mg/mL Ti₃C₂T_x-MXene/EP composite sizing agent sized carbon fibers
D-HMCF/EP		Desized BHM2 carbon fiber reinforced epoxy composites
U-HMCF/EP		BHM2 carbon fiber reinforced epoxy composites
Ti₃C₂T_x-0MXene-SCF/EP		0 mg/mL Ti₃C₂T_x-MXene/EP composite sizing agent sized carbon fiber reinforced epoxy composites
Ti₃C₂T_x-0.5MXene-SCF/EP		0.5 mg/mL Ti₃C₂T_x-MXene/EP composite sizing agent sized carbon fiber reinforced epoxy composites
Ti₃C₂T_x-1.0MXene-SCF/EP		1.0 mg/mL Ti₃C₂T_x-MXene/EP composite sizing agent sized carbon fiber reinforced epoxy composites
Ti₃C₂T_x-1.5MXene-SCF/EP		1.5 mg/mL Ti₃C₂T_x-MXene/EP composite sizing agent sized carbon fiber reinforced epoxy composites
Ti₃C₂T_x-2.0MXene-SCF/EP		2.0 mg/mL Ti₃C₂T_x-MXene/EP composite sizing agent sized carbon fiber reinforced epoxy composites

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表 2 不同HMCF的C1s特征峰结合能及相对含量

Table 2. C1s characteristic peak binding energy and relative content of different HMCF

Functional group	Binding energy/eV	Relative content/%
Functional group	Binding energy/eV	D-HMCF/%	Ti₃C₂T_x-0MXene-SCF/%	Ti₃C₂T_x-1.0MXene-SCF/%
Ti—C(MXene)	281.9	—	—	3.25
C—C	284.6	46.00	45.69	38.37
—HC—CH—	285.5	39.25	37.81	35.10
C—O	286.4	2.37	4.51	15.34
C=O	287.3	3.40	11.46	6.84
—COOH	288.6	3.03	—	—
π*-π	290.8	5.95	0.53	1.08

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