Reversible surface modification of PAN-based carbon fibers by a ferrocene-based surfactant
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摘要: 采用电化学可逆表面活性剂（二茂铁）十二烷基二甲基溴化铵（FDDA）对炭纤维进行表面改性。结果表明，FDDA能够在炭纤维表面进行吸附及电化学脱附，实现可逆的表面改性。同时证实了FDDA主要通过非静电相互作用在炭纤维表面以多分子层的方式进行吸附。此外，通过单丝拉伸断裂法探究了FDDA改性炭纤维对炭纤维/环氧树脂界面性能的影响。与未改性的炭纤维相比，FDDA改性的炭纤维与环氧树脂之间的界面黏结性能得到明显改善。Abstract: The surface of carbon fibers (CFs) was modified by a surfactant (ferrocenemethyl)dodecyldimethylammonium bromide (FDDA) to enhance the interfacial ashesion between the CFs and surrounding matrix. Results showed that it could be electrochemically desorbed by a potentiostatic electro-oxidation method. The FDDA adsorption isotherm was attributed to the formation of multi-molecular layers mainly by non-electrostatic interactions. The adsorption and desorption of FDDA on the CFs have little effect on their tensile strength. The effects of FDDA modification on the interfacial properties of CF/epoxy composites were evaluated by a single-filament fragmentation test. Compared with the un-modified CFs, the FDDA-modified ones had significantly improved interfacial adhesion properties in the composites. This method provides a potential approach for preparing recyclable CF/resin composites.
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Key words:
- Carbon fibers /
- FDDA /
- Reversible modification /
- Interfacial properties
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Figure 2. SEM images of CFs: (a) before adsorption, (b) after adsorption (0.8 mmol/L, lower than CMC), (c) after adsorption (1.6 mmol/L, higher than CMC), (d) after adsorption and electrochemical desorption
Figure 3. FDDA adsorption isotherm for CFs and the fitting curve with the Langmuir (solid line) and Freundlich (dotted line) models
Figure 5. (a) Effect of pH value on the adsorption of FDDA on the CFs and (b) Narrow spectrum of N1s region
Figure 6. The tensile strength Weibull distribution curves for (a) bare CFs, (b) FDDA-adsorbed CFs, (c) FDDA-adsorbed and then electrochemically desorbed CFs
Figure 7. The optical photos and corresponding contact angles of epoxy resin droplets on (a) the as-received CFs and (b) the FDDA-adsorbed CFs
Figure 8. The birefringence patterns of the unidirectional single-CF model composites after single-filament tensile fragmentation tests: (a) the as-received CFs and (b) the FDDA-adsorbed CFs
Table 1. The relative contents of surface elements on the CFs
Element
content/%CFs Before
adsorptionAfter
adsorptionAfter adsorption
and desorptionC 87.08 86.78 80.85 O 9.73 8.12 14.90 N 3.20 3.59 3.37 Fe - 1.50 0.88 
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Table 2. Thermodynamics parameters for the adsorption of FDDA on the CFs
T
/(K)Kc
/(L/kg)$\Delta {G}_{m}^{\theta } $
/(kJ/mol)$\Delta {H}_{m}^{\theta } $
/(kJ/mol)$\Delta {S}_{m}^{\theta } $
/(J/(mol·K))293.5 58.21 −9.91 −3.65 21.19 303.5 53.09 −10.02 308.5 52.45 −10.15 313.5 52.45 −10.32 318.5 51.18 −10.42 323.5 49.91 −10.51
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