碳纳米管对炭纤维/聚碳酸酯复合材料界面结合性能的影响

刘玉婷; 李璐; 王嘉沛; 费滢洁; 刘牛顿; 吴刚平

doi:10.1016/S1872-5805(21)60035-5

碳纳米管对炭纤维/聚碳酸酯复合材料界面结合性能的影响

doi: 10.1016/S1872-5805(21)60035-5

刘玉婷^{1, 2, 3,},
李璐⁴,
王嘉沛⁴,
费滢洁⁴,
刘牛顿⁴,
吴刚平^{1, 2, 3, ,}

1.
中国科学院山西煤炭化学研究所，碳纤维制备技术国家工程实验室，山西太原 030001
2.
中国科学院大学，材料与光电研究中心，北京 100049
3.
中国科学院山西煤炭化学研究所，炭材料重点实验室，山西太原 030001
4.
太原理工大学化学化工学院，山西太原 030024

基金项目: 国家自然科学基金委-山西煤基低碳联合基金（U1810116），山西省科技重大专项项目（20181101020），山西省应用基础研究计划（201901D211587），山西省重点研发计划（201903D121004, 201903D121102）。

详细信息

作者简介:
刘玉婷，硕士. E-mail：liuyuting@sxicc.ac.cn

通讯作者:
吴刚平，博士，研究员. E-mail：wgp@sxicc.ac.cn

中图分类号: TB33
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- 被引次数: 0
出版历程
- 收稿日期: 2018-06-25
- 修回日期: 2019-10-28
- 网络出版日期: 2021-04-06
- 刊出日期: 2021-06-01

Effect of carbon nanotubes on interfacial properties of a carbon fiber / polycarbonate composite

LIU Yu-ting^{1, 2, 3
,},
LI Lu⁴,
WANG Jia-pei⁴,
FEI Ying-jie⁴,
LIU Niu-dun⁴,
WU Gang-ping^{1, 2, 3
, ,}

1.
National Engineering Laboratory for Carbon Fiber Technology, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
3.
CAS Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
4.
College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China

Funds: National Natural Science Foundation of China -Shanxi Coal-based Low Carbon Joint Fund (U1810116); Major Science and Technology Projects of Shanxi Province (20181101020); Applied Fundamental Research Project of Shanxi Province (201901D211587); Key Research & Development Project of Shanxi Province (201903D121004, 201903D121102).

More Information

Corresponding author: WU Gang-ping, Ph. D, Professor. E-mail: wgp@sxicc.ac.cn

摘要

摘要: 为改善炭纤维和聚碳酸酯界面结合性能，制备了含碳纳米管的水性聚碳酸酯上浆剂和水性聚氨酯上浆剂，通过上浆工艺将碳纳米管引至炭纤维表面。分别采用单丝段裂法和定向纤维增强聚合物基复合材料垂直方向拉伸两种方法从微观和宏观两个角度研究了上浆剂种类及碳纳米管含量对复合材料界面结合性能的影响。结果表明：上浆剂可明显改善炭纤维/聚碳酸酯复合材料界面结合性能，由于优异的成膜性，聚氨酯上浆剂改善效果更明显；碳纳米管的加入对复合材料的界面性能有一定改善，在微观评价方法中，碳纳米管改善效果显著，因为碳纳米管可有效阻止界面滑移；在宏观评价中，碳纳米管改善效果不明显，主要是上浆剂的界面黏结发挥作用。
- 碳纳米管 /
- 上浆剂 /
- 炭纤维 /
- 聚碳酸酯 /
- 界面
Abstract: In order to improve interfacial bonding between carbon fiber (CF) and polycarbonate (PC), sizing agents of water-borne polycarbonate (WPC) and water-borne polyurethane (WPU) containing carbon nanotubes (CNTs) were used to treat the CFs. CNTs were introduced onto the surfaces of the CFs by a sizing process. The effects of sizing agents and CNT content on the interfacial properties of the composites were investigated by two methods, a single fiber fragmentation test (SFFT) for the monofilament reinforced composite and a transverse tensile test for the directional bundle composite. The results show that WPU is more conducive to improving the interfacial bonding properties of CF/PC composites because of its film-forming property, and the addition of CNTs has a beneficial effect on the interfacial properties of the composites. CNTs can effectively prevent interfacial slip and therefore significantly improve the interfacial properties in the SFFT, while the improvement is not obvious in a transverse tensile test because the adhesion of sizing agents plays a leading role.
- Carbon nanotubes /
- Sizing agent /
- Carbon fiber /
- Polycarbonate /
- Interface

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FIG. 681. FIG. 681.

FIG. 681.. FIG. 681.

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图 1 含CNTs上浆剂制备及上浆工艺示意图

Figure 1. Schematic diagram preparation of sizing agent containing CNTs and the sizing process.

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图 2 样品及受力示意图：单丝段裂法（左）；90°拉伸（右）（尺寸单位：mm）

Figure 2. The diagram of sample for single filament split method (left); transvers tensile (right) (size in mm).

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图 3 上浆剂处理前后炭纤维表面XPS光谱（上）及C 1s窄扫并分峰拟合结果（下）

Figure 3. XPS spectra of carbon fiber surface (up) and C 1s narrow sweep and peak-splitting fitting results (down) before and after sizing.

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图 4 SEM照片：(a) 未上浆炭纤维CF；(b~f) PU上浆剂处理纤维，依次为CF₀，CF_0.05，CF_0.1，CF_0.2，CF_0.3；(g~j) PC上浆剂处理纤维，依次为CF₀，CF_0.05，CF_0.1，CF_0.2

Figure 4. SEM images of CFs: (a) CF；(b–f) Fibers treated with PU sizing agent, from left to right，CF₀，CF_0.05，CF_0.1，CF_0.2，CF_0.3；(g–j) PC sizing agent, from left to right，CF₀，CF_0.05，CF_0.1，CF_0.2.

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图 5 不同炭纤维表面能γ及其各分量

Figure 5. Surface energy and corresponding components of CFs.

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图 6 临界饱和状态双折射现象: (a) CF；(b) CF₀（WPU）；(c) CF₀（WPC）；(d) CF_0.1（WPU）；(e) CF_0.1（WPC）及断点示意图: (f) 较弱结合；(g) 较强结合

Figure 6. Birefringence patterns obtained at the saturation state: (a) CF；(b) CF₀(WPU); (c) CF₀(WPC); (d) CF_0.1(WPU); (e) CF_0.1(WPC) and the model diagram of breakpoint morphology: (f) weaker combination, (g) stronger combination.

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图 7 单丝段裂法所测得的界面结合强度

Figure 7. The interfacial bonding strength obtained by SFFT.

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图 8 界面结合强度评价方法作用模型：（左）单丝段裂法；（右）90°拉伸

Figure 8. The model for evaluation methods of interfacial bonding strength: (left) SFFT; (right) Transvers tensile.

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表 1 上浆剂处理前后炭纤维表面官能团种类及含量

Table 1. The species and contents of functional groups on carbon fiber before and after sizing.

Functional group (Bind energy (eV))	CF	WPU	WPC
C＝C, C―C (284.4–284.8)	80.79	48.47	76.18
C―O (286.1–286.5)	15.32	36.30	11.86
C＝O (287.4–288.0)	3.89	10.21	-
O―C＝O (288.4–288.9)	-	5.02	8.85
O―C(O)―O (290.4–290.8)	-	-	3.11

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表 2 通过原子力显微镜测得炭纤维表面粗糙度R_a (nm)

Table 2. The surface roughness of CFs via AFM R_a (nm).

CNT (wt%)	As-received CF	0	0.05	0.1	0.2	0.3
WPU	39.42	33.25	89.25	102.35	125.68	498.32
WPC	39.42	32.96	93.65	121.37	136.98	632.69

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表 3 CF单丝拉伸性能及Weibull模量

Table 3. Tensile properties and Weibull modulus.

CF	WPU		WPC
CF	σ_f / GPa	m	σ_f / GPa	m
CF	2.55 ± 0.52	6.069	2.55 ± 0.52	6.069
CF₀	2.79 ± 0.43	6.542	2.77 ± 0.56	6.057
CF_0.05	2.71 ± 0.56	6.150	2.69 ± 0.60	6.946
CF_0.1	2.73 ± 0.50	6.881	2.70 ± 0.48	6.767
CF_0.2	2.73 ± 0.52	6.989	2.72 ± 0.55	7.632

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表 4 DCAT-21测量不同炭纤维在测试液体动态接触角（单位：°）

Table 4. Dynamic contact angle of carbon fibers with two different test liquids via DCAT-21 (Unit is degree).

CF	WPU		WPC
CF	Water	DIM	Water	DIM
CF	75.32 ± 0.24	40.30 ± 0.18	75.32 ± 0.24	36.60 ± 0.18
CF₀	63.38 ± 0.16	40.81 ± 0.15	63.98 ± 0.15	40.35 ± 0.10
CF_0.05	64.29 ± 0.19	36.45 ± 0.16	64.32 ± 0.19	36.42 ± 0.15
CF_0.1	64.67 ± 0.19	36.38 ± 0.15	64.75 ± 0.21	36.29 ± 0.13
CF_0.2	65.07 ± 0.23	36.35 ± 0.16	65.04 ± 0.19	36.29 ± 0.20

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表 5 定向CF/PC复合材料垂直拉伸结果

Table 5. The results of vertical direction stretching for CF/PC composite.

CF	WPU			WPC
CF	σ_t/MPa	Increase/%	E_t/GPa	σ_t/MPa	Increase/%	E_t/GPa
CF	49.02 ± 2.67	-	1.79 ± 0.09	49.02 ± 2.67	-	1.79 ± 0.09
CF₀	57.65 ± 2.08	17.61	1.88 ± 0.05	57.77 ± 2.11	17.85	2.14 ± 0.06
CF_0.05	58.40 ± 1.89	19.14	1.96 ± 0.08	58.02 ± 2.55	18.36	1.72 ± 0.09
CF_0.1	59.56 ± 2.60	21.50	1.78 ± 0.09	58.40 ± 2.86	19.13	1.61 ± 0.09
CF_0.2	55.51 ± 2.92	13.24	1.52 ± 0.08	54.60 ± 1.25	11.38	1.49 ± 0.09
CF_0.3	46.52 ± 2.35	−5.10	1.51 ± 0.05	44.10 ± 2.27	−10.04	1.57 ± 0.06

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