Graphene nanoplatelet-modified epoxy: effect of aspect ratio and surface functionality on mechanical properties and toughening mechanisms
Source abstract
Abstract
Graphene has the potential to act as a high-performance reinforcement for adhesives or fibre composites when combined with epoxy polymer. However, it is currently mostly available not as single high aspect ratio sheets but as graphene nanoplatelets (GNPs), comprising stacks of graphene sheets. GNPs of a range of lateral size, thickness, aspect ratio and surface functionality were used to modify an anhydride-cured epoxy polymer. The morphology, mechanical properties and toughening mechanisms of these modified epoxies were investigated. The GNPs were sonicated in tetrahydrofuran (THF) or n-methyl-pyrrolidone (NMP) to facilitate dispersion in the epoxy. The use of THF resulted in large agglomerates, whereas more finely dispersed stacks of GNPs were observed for NMP. The maximum values of modulus (3.6 GPa at 1 wt%) and fracture energy (343 J/m\(^2\) at 2 wt%) were measured for the epoxy modified with an intermediate platelet size of approximately 4 \(\upmu \)m, compared to 2.9 GPa and 96 J/m\(^2,\) respectively, for the unmodified epoxy. The Young’s modulus was highly dependent on the dispersion quality, whereas the fracture energy was independent of the degree of GNP dispersion. The larger agglomerates of the GNPs which were dispersed in THF toughened the epoxy by crack deflection, whereas the GNPs dispersed in NMP showed platelet debonding, pull-out and plastic void growth of the epoxy. This work indicates that reinforcement and toughening can be achieved at much lower contents than for conventional modifiers. Further, achieving a good dispersion is crucial to the engineering application of these materials, and intermediate-sized graphene achieves the best balance of properties.
Source: openaire · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Fiber-reinforced polymer composites · Graphene research and applications · Epoxy Resin Curing Processes
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (58)
Show source-provided references
1. Bagheri R, Marouf BT, Pearson RA (2009) Rubber-toughened epoxies: a critical review. Polym Rev 49(3):201–225. doi: 10.1080/1558372090304822710.1080/15583720903048227 ↗
2. Sprenger S (2013) Epoxy resins modified with elastomers and surface-modified silica nanoparticles. Polymer 54(18):4790–4797. doi: 10.1016/j.polymer.2013.06.01110.1016/j.polymer.2013.06.011 ↗
3. Kim H, Miura Y, Macosko CW (2010a) Graphene/polyurethane nanocomposites for improved gas barrier and electrical conductivity. Chem Mater 22(11):3441–3450. doi: 10.1021/cm100477v10.1021/cm100477v ↗
4. Vuluga D, Thomassin JM, Molenberg I, Huynen I, Gilbert B, Jerome C, Alexandre M, Detrembleur C (2011) Straightforward synthesis of conductive graphene/polymer nanocomposites from graphite oxide. Chem Commun 47(9):2544–2546. doi: 10.1039/C0CC04623J10.1039/C0CC04623J ↗
5. Young RJ, Kinloch IA, Gong L, Novoselov KS (2012) The mechanics of graphene nanocomposites: a review. Compos Sci Technol 72(12):1459–1476. doi: 10.1016/j.compscitech.2012.05.00510.1016/j.compscitech.2012.05.005 ↗
6. Potts JR, Dreyer DR, Bielawski CW, Ruoff RS (2011) Graphene-based polymer nanocomposites. Polymer 52(1):5–25. doi: 10.1016/j.polymer.2010.11.04210.1016/j.polymer.2010.11.042 ↗
7. Bortz DR, Heras EG, Martin-Gullon I (2011) Impressive fatigue life and fracture toughness improvements in graphene oxide/epoxy composites. Macromolecules 45(1):238–245. doi: 10.1021/ma201563k10.1021/ma201563k ↗
8. Bao C, Guo Y, Song L, Kan Y, Qian X, Hu Y (2011) In situ preparation of functionalized graphene oxide/epoxy nanocomposites with effective reinforcements. J Mater Chem 21(35):13290. doi: 10.1039/C1JM11434D10.1039/C1JM11434D ↗
9. Liu Q, Zhou X, Fan X, Zhu C, Yao X, Liu Z (2012) Mechanical and thermal properties of epoxy resin nanocomposites reinforced with graphene oxide. Polym Plast Technol Eng 51(3):251–256. doi: 10.1080/03602559.2011.62538110.1080/03602559.2011.625381 ↗
10. Ramos-Galicia L, Mendez LN, Martfnez-Hernndez AL, Espindola-Gonzalez A, Galindo-Esquivel IR, Fuentes-Ramirez R, Velasco-Santos C (2013) Improved performance of an epoxy matrix as a result of combining graphene oxide and reduced graphene. Int J Polym Sci 1–7:2013. doi: 10.1155/2013/49314710.1155/2013/493147 ↗
11. Kim H, Abdala AA, Macosko CW (2010b) Graphene/polymer nanocomposites. Macromolecules 43(16):6515–6530. doi: 10.1021/ma100572e10.1021/ma100572e ↗
12. Chatterjee S, Nafezarefi F, Tai NH, Schlagenhauf L, Nnesch FA, Chu BTT (2012) Size and synergy effects of nanofiller hybrids including graphene nanoplatelets and carbon nanotubes in mechanical properties of epoxy composites. Carbon 50(15):5380–5386. doi: 10.1016/j.carbon.2012.07.02110.1016/j.carbon.2012.07.021 ↗
13. Rafiee MA, Rafiee J, Wang Z, Song H, Yu ZZ, Koratkar N (2009) Enhanced mechanical properties of nanocomposites at low graphene content. ACS Nano 3(12):3884–3890. doi: 10.1021/nn901047210.1021/nn9010472 ↗
14. Zaman I, Phan TT, Kuan H-C, Meng Q, La LTB, Luong L, Youssf O, Ma J (2011) Epoxy/graphene platelets nanocomposites with two levels of interface strength. Polymer 52(7):1603–1611. doi: 10.1016/j.polymer.2011.02.00310.1016/j.polymer.2011.02.003 ↗
15. Zaman I, Kuan HC, Dai J, Kawashima N, Michelmore A, Sovi A, Dong S, Luong L, Ma J (2012) From carbon nanotubes and silicate layers to graphene platelets for polymer nanocomposites. Nanoscale 4(15):4578–86. doi: 10.1039/c2nr30837a10.1039/c2nr30837a ↗
16. Haydale Ltd. (2013a) HDPlas™GNP-COOH Technical data sheet. Haydale Ltd, Carmarthenshire
17. Haydale Ltd. (2013b) HDPlas™GNP-O $$_2$$ 2 Technical data sheet. Haydale Ltd, Carmarthenshire
18. XG Sciences (2013a) xGnP Grade C product characteristics. XG Sciences, Lansing
19. XG Sciences (2013b) xGnP Grade H product characteristics. XG Sciences, Lansing
20. XG Sciences (2013c) xGnP Grade M product characteristics. XG Sciences, Lansing
21. Graphene Supermarket. Graphene Nanopowder: 12 nm Flakes-25 g. [Online]. https://graphene-supermarket.com/Graphene-Nanopowder-12-nm-Flakes-5-g-S KU-NP-FLAO3-5G11.html . Accessed 23 June 2014
22. Drzal LT (2005) Graphite nanoreinforcements for aerospace nanocomposites. Final Report for NASA Langley Research Center, NAG1-01004
23. Scherrer P (1918) Bestimmung der grösse und der inneren struktur von kolloidteilchen mittels röntgenstrahlen. Nachrichten von der Gesellschaft der Wissenschaften zu Göttingen. Mathematisch-Physikalische Klasse 26:98–100
24. Watts JF, Wolstenholme J (2003) An introduction to surface analysis by XPS and AES. Wiley, New York. doi: 10.1002/047086793010.1002/0470867930 ↗
25. ISO 527-2 (1996) Plastics—determination of tensile properties—Part 2: test conditions for moulding and extrusion plastics. International Standards Organisation, Geneva
26. Williams JG, Ford H (1964) Stress-strain relationships for some unreinforced plastics. J Mech Eng Sci 6(4):405–417. doi: 10.1243/JMES_JOUR_1964_006_055_0210.1243/JMES_JOUR_1964_006_055_02 ↗
27. Bowden PB, Raha S (1970) The formation of micro shear bands in polystyrene and polymethylmethacrylate. Philos Mag 22(177):463–482. doi: 10.1080/1478643700822583710.1080/14786437008225837 ↗
28. Huang Y, Kinloch AJ (1992) Modelling of the toughening mechanisms in rubber-modified epoxy polymers. Part II. A quantitative description of the microstructure-fracture property relationships. J Mater Sci 27:2763–2769. doi: 10.1007/BF0054070310.1007/BF00540703 ↗
29. Sultan JN, McGarry FJ (1973) Effect of rubber particle size on deformation mechanisms in glassy epoxy. Polym Eng Sci 13(1):29–34. doi: 10.1002/pen.76013010510.1002/pen.760130105 ↗
30. ISO 13586 (2000) Plastics—determination of fracture toughness ( $$GIC$$ G I C and $$KIC$$ K I C )—linear elastic fracture mechanics (LEFM) approach. International Standards Organisation, Geneva
31. Lukesh JS, Pauling L (1950) The problem of the graphite structure. Am Mineral 35:125
32. Ivanovskaya VV, Wagner P, Zobelli A, Suarez-Martinez I, Yaya A, Ewels CP (2012) Graphene edge structures: folding, scrolling, tubing, rippling and twisting, chapter 10. Carbon nanostructures. Springer, Berlin, pp 75–85. doi: 10.1007/978-3-642-20644-3_1010.1007/978-3-642-20644-3_10 ↗
33. Beamson G, Briggs D (1992) High resolution XPS of organic polymers: the Scienta ESCA300 database. Wiley, New York. doi: 10.1021/ed070pA25.510.1021/ed070pA25.5 ↗
34. Kinloch AJ, Taylor AC (2006) The mechanical properties and fracture behaviour of epoxy-inorganic micro- and nano-composites. J Mater Sci 41(11):3271–3297. doi: 10.1007/s10853-005-5472-010.1007/s10853-005-5472-0 ↗
35. Zaldivar RJ, Nokes JP, Adams PM, Hammoud K, Kim HI (2012) Surface functionalization without lattice degradation of highly crystalline nanoscaled carbon materials using a carbon monoxide atmospheric plasma treatment. Carbon 50(8):2966–2975. doi: 10.1016/j.carbon.2012.02.07910.1016/j.carbon.2012.02.079 ↗
36. Tillet G, Boutevin B, Ameduri B (2011) Chemical reactions of polymer crosslinking and post-crosslinking at room and medium temperature. Prog Polym Sci 36(2):191–217. doi: 10.1016/j.progpolymsci.2010.08.00310.1016/j.progpolymsci.2010.08.003 ↗
37. Lee C, Wei X, Kysar JW, Hone J (2008) Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321(5887):385–8. doi: 10.1126/science.115799610.1126/science.1157996 ↗
38. Andrews EH (1968) Fractures in polymer. Oliver & Boyd, Edinburgh
39. Faber KT, Evans AG (1983) Crack deflection processes I. Theory Acta Metall 31(4):565–576. doi: 10.1016/0001-6160(83)90046-910.1016/0001-6160(83)90046-9 ↗
40. Hsieh TH, Kinloch AJ, Masania K, Lee JS, Taylor AC, Sprenger S (2010) The toughness of epoxy polymers and fibre composites modified with rubber microparticles and silica nanoparticles. J Mater Sci 45(5):1193–1210. doi: 10.1007/s10853-009-4064-910.1007/s10853-009-4064-9 ↗
41. Gao XL, Li K (2005) A shear-lag model for carbon nanotube-reinforced polymer composites. Int J Solids Struct 42(5–6):1649–1667. doi: 10.1016/j.ijsolstr.2004.08.02010.1016/j.ijsolstr.2004.08.020 ↗
42. Hernandez Y, Nicolosi V, Lotya M, Blighe FM, Sun Z, De S, McGovern IT, Holland B, Byrne M, Gun’Ko YK, Boland JJ, Niraj P, Duesberg G, Krishnamurthy S, Goodhue R, Hutchison J, Scardaci V, Ferrari AC, Coleman JN (2008) High-yield production of graphene by liquid-phase exfoliation of graphite. Nat Nanotechnol 3(9):563–568. doi: 10.1038/nnano.2008.21510.1038/nnano.2008.215 ↗
43. Zhao W, Wu F, Wu H, Chen G (2010) Preparation of colloidal dispersions of graphene sheets in organic solvents by using ball milling. J Nanomater 2010(528325):1–5. doi: 10.1155/2010/52823510.1155/2010/528235 ↗
44. Pearson RA, Yee AF (1991) Influence of particle size and particle size distribution on toughening mechanisms in rubber-modified epoxies. J Mater Sci 26(14):3828–3844. doi: 10.1007/BF0118497910.1007/BF01184979 ↗
45. Guild FJ, Kinloch AJ, Taylor AC (2010) Particle cavitation in rubber toughened epoxies: the role of particle size. J Mater Sci 45(14):3882–3894. doi: 10.1007/s10853-010-4447-y10.1007/s10853-010-4447-y ↗
46. Lee Y, Bae S, Jang H, Jang S, Zhu S-E, Sim SH, Song YI, Hong BH, Ahn J-H (2010) Wafer-scale synthesis and transfer of graphene films. Nano Lett 10(2):490–493. doi: 10.1021/nl903272n10.1021/nl903272n ↗
47. Herceg T, Abidin MSZ, Delfour C, Greenhalgh E, Bismarck A, Shaffer M (2013) Scalable production of epoxy based nanocomposites and hierarchical composites with high CNT loadings. 19th international conference on composite materials, 28 July–2 August 2013, Montreal, Canada
48. Halpin JC, Pagano NJ (1969) The laminate approximation for randomly oriented fibrous composites. J Compos Mater 3(4):720–724. doi: 10.1177/00219983690030041610.1177/002199836900300416 ↗
49. Halpin JC, Kardos JL (1976) The Halpin–Tsai equations: a review. Polym Eng Sci 16(5):344–352. doi: 10.1002/pen.76016051210.1002/pen.760160512 ↗
50. Van Es MA (2001) Polymer-clay nanocomposites: the importance of particle dimensions. PhD Thesis, Faculty of Applied Sciences, Delft University of Technology
51. Mori T, Tanaka K (1973) Average stress in matrix and average elastic energy of materials with misfitting inclusions. Acta Metall 21(5):571–574. doi: 10.1016/0001-6160(73)90064-310.1016/0001-6160(73)90064-3 ↗
52. Tandon GP, Weng GJ (1984) The effect of aspect ratio of inclusions on the elastic properties of unidireectionally aligned composites. Polym Compos 5(4):327–333. doi: 10.1002/pc.75005041310.1002/pc.750050413 ↗
53. Hsieh TH, Kinloch AJ, Taylor AC, Kinloch IA (2011) The effect of carbon nanotubes on the fracture toughness and fatigue performance of a thermosetting epoxy polymer. J Mater Sci 46(23):7525–7535. doi: 10.1007/s10853-011-5724-010.1007/s10853-011-5724-0 ↗
54. Green DJ, Nicholson PS, Embury JD (1979) Fracture of a brittle particulate composite. Part 1. Experimental aspects. J Mater Sci 14(6):1413–1420. doi: 10.1016/0010-4361(79)90034-X10.1016/0010-4361(79)90034-X ↗
55. Johnsen BB, Kinloch AJ, Mohammed RD, Taylor AC, Sprenger S (2007) Toughening mechanisms of nanoparticle-modified epoxy polymers. Polymer 48(2):530–541. doi: 10.1016/j.polymer.2006.11.03810.1016/j.polymer.2006.11.038 ↗
56. Hull D, Clyne TW (1981) An introduction to composite materials. Cambridge University Press, Cambridge
57. Barber AH, Cohen SR, Kenig S, Wagner HD (2004) Interfacial fracture energy measurements for multi-walled carbon nanotubes pulled from a polymer matrix. Compos Sci Technol 64(15):2283–2289. doi: 10.1016/j.compscitech.2004.01.02310.1016/j.compscitech.2004.01.023 ↗
58. Kinloch AJ, Taylor AC (2002) The toughening of cyanate-ester polymers. Part I Physical modification using particles, fibres and woven-mats. J Mater Sci 37(3):433–460. doi: 10.1023/A:101373510312010.1023/A:1013735103120 ↗