Abstract
This paper provides a continuous method for grafting carbon nanotubes (CNTs) on the surface of carbon fibers by chemical vapor deposition (CVD). The control of the morphology of CNTs/CFs can be achieved by adding thiourea to the cobalt nitrate precursor. The sulfur can increase the catalytic activity of the Co catalyst. Scanning electron microscopy reveals that a uniform layer of CNTs is grafted onto the surface of carbon fibers with the presence of thiourea. Through the single-filament tensile strength test, it can be found that the tensile strength of the fiber is increased by up to about 10% compared with the desized carbon fibers after the CVD process. And the reason for the enhancement is explored through X-ray diffraction. Raman spectroscopy reveals that the sample possesses the highest degree of graphitization at a thiourea concentration of 0.02 mol/L. It is found by high-resolution transmission electron microscopy that the growth mechanism of CNTs is tip growth mechanism, and the diameter of the CNTs is about 15 nm.
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References
Islam MS, Deng Y, Tong L et al (2016) Grafting carbon nanotubes directly onto carbon fibers for superior mechanical stability: towards next generation aerospace composites and energy storage applications. Carbon 96:701–710
Cui HZ, Jin ZY, Zheng DP et al (2018) Effect of carbon fibers grafted with carbon nanotubes on mechanical properties of cement-based composites. Constr Build Mater 181:713–720
Shen QL, Li HJ, Li W et al (2018) Realizing the synergy of carbon nanotubes and matrix microstructure for improved flexural behavior of laminated carbon/carbon composites. J Alloy Compd 738:49–55
Li R, Lachman N, Florin P et al (2015) Hierarchical carbon nanotube carbon fiber unidirectional composites with preserved tensile and interfacial properties. Compos Sci Technol 117:139–145
Tsirka K, Tzounis L, Avgeropoulos A et al (2018) Optimal synergy between micro and nano scale: hierarchical all carbon composite fibers for enhanced stiffness, interfacial shear strength and Raman strain sensing. Compos Sci Technol 165:240–249
Yan F, Liu L, Li M et al (2018) Preparation of carbon nanotube/copper/carbon fiber hierarchical composites by electrophoretic deposition for enhanced thermal conductivity and interfacial properties. J Mater Sci 53:8108–8119. https://doi.org/10.1007/s10853-018-2115-9
Zheng LB, Wang YX, Qin JJ et al (2018) Scalable manufacturing of carbon nanotubes on continuous carbon fibers surface from chemical vapor deposition. Vacuum 152:84–90
Xu F, Liu HY, Du XS (2018) An analytical model of interlaminar fracture of polymer composite reinforced by carbon fibres grafted with carbon nanotubes. Polymers 10:683
Romanov VS, Lomov SV, Verpoest I et al (2015) Modelling evidence of stress concentration mitigation at the micro-scale in polymer composites by the addition of carbon nanotubes. Carbon 82:184–194
Romanov VS, Lomov SV, Verpoest I et al (2014) Can carbon nanotubes grown on fibers fundamentally change stress distribution in a composite? Compos Part A: Appl Sci Manuf 63:32–34
Wang BB, Fu QG, Yin T et al (2018) Grafting CNTs on carbon fabrics with enhanced mechanical and thermal properties for tribological applications of carbon fabrics/phenolic composites. Carbon 139:45–51
Song Q, Li KZ, Li HJ et al (2013) A novel method to fabricate isotropic pyrocarbon by densifying a multi-walled carbon nanotube preform by fixed-bed chemical vapor deposition. Carbon 59:547–550
Mittal G, Rhee KY (2018) Chemical vapor deposition-based grafting of CNTs onto basalt fabric and their reinforcement in epoxy-based composites. Compos Sci Technol 165:84–94
Han LY, Li KZ, Sun JJ et al (2018) Reinforcing effects of carbon nanotube on carbon/carbon composites before and after heat treatment. Mater Sci Eng A 735:10–18
Feng L, Li KZ, Xue B et al (2017) Optimizing matrix and fiber/matrix interface to achieve combination of strength, ductility and toughness in carbon nanotube-reinforced carbon/carbon composites. Mater Des 113:9–16
Qin J, Wang C, Wang Y et al (2018) Synthesis and growth mechanism of carbon nanotubes growing on carbon fiber surfaces with improved tensile strength. Nanotechnology 29(39):395602
Anthony DB, Sui XM, Kellersztein I et al (2018) Continuous carbon nanotube synthesis on charged carbon fibers. Compos Part A Appl Sci Manuf 112:525–538
Hwang S, Kim S, Cho GB et al (2018) Carbon nanotubes radially anchored on carbon fibers formed by polyacrylonitrile. Mater Res Bull 97:49–55
Maruyama T, Kozawa A, Saida T et al (2017) Low temperature growth of single-walled carbon nanotubes from Rh catalysts. Carbon 116:128–132
Bouanis FZ, Florea I, Bouanis M et al (2018) Diameter controlled growth of SWCNTs using Ru as catalyst precursors coupled with atomic hydrogen treatment. Chem Eng J 332:92–101
Jourdain V, Bichara C (2013) Current understanding of the growth of carbon nanotubes in catalytic chemical vapour deposition. Carbon 58:2–39
Deng Y, Islam MS, Tong LY (2018) Effects of grafting strength and density on interfacial shear strength of carbon nanotube grafted carbon fibre reinforced composites. Compos Sci Technol 168:195–202
Khan S, Bedi HS, Agnihotri PK (2018) Augmenting mode-II fracture toughness of carbon fiber/epoxy composites through carbon nanotube grafting. Eng Fract Mech 204:211–220
Lu RJ, Wang CG, Wang YX et al (2018) A CVD method for preparing CNTs-grafted carbon fiber fabrics under quasi-vacuum at low temperature. ECS J Solid State Sci Technol 7:M49–M53
Anthony DB, Qian H, Clancy AJ et al (2017) Applying a potential difference to minimise damage to carbon fibres during carbon nanotube grafting by chemical vapour deposition. Nanotechnology 28:305–602
Wang XH, Wang CG, Wang ZY et al (2018) Colossal permittivity of carbon nanotubes grafted carbon fiber-reinforced epoxy composites. Mater Lett 211:273–276
Lee SH, Park J, Kim HR et al (2015) Synthesis of high-quality carbon nanotube fibers by controlling the effects of sulfur on the catalyst agglomeration during the direct spinning process. RSC Adv 5:41894–41900
Suzuki S, Mori S (2018) Impacts of different sulfur sources as a promoter on the growth of carbon nanotubes in chemical vapor deposition. Chem Phys Lett 709:1–6
Kim KJ, Yu WR, Youk JH et al (2012) Degradation and healing mechanisms of carbon fibers during the catalytic growth of carbon nanotubes on their surfaces. ACS Appl Mater Interfaces 4:2250–2258
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This work was supported by the Natural Science Foundation in Shandong Province (ZR2017MEM011, 2018GGX104022, 2018GGX102031), the National Natural Science Foundation of China (51773110, 51573087).
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Su, S., Wang, Y., Qin, J. et al. Continuous method for grafting CNTs on the surface of carbon fibers based on cobalt catalyst assisted by thiourea. J Mater Sci 54, 12498–12508 (2019). https://doi.org/10.1007/s10853-019-03827-8
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DOI: https://doi.org/10.1007/s10853-019-03827-8