Influence of different functionalization methods of multi-walled carbon nanotubes on the properties of poly(L-lactide) based nanocomposites

Nevena Vukić, Ivan S Ristić, Milena Marinović-Cincović, Radmila Radičević, Branka Pilić, Suzana Cakić, Jaroslava Budinski-Simendić


This paper presents influence of the type of carbon nanotube functionalization on properties of poly(L-lactide) (PLLA) based nanocomposite materials. For this purpose surface modifications of multi-walled carbon nanotubes (MWCNTs) were performed by chemical and irradiation techniques, while thermo gravimetric analysis, UV-Visible and Fourier-transform infrared (FT-IR) spectroscopies confirmed successful covalent functionalization. Series of PLLA bionano­com­posites with different contents of functionalized MWCNTs (0.7; 1.6; 2.1 wt%), were synthesized via ring-opening solution polymerisation of L-lactide. FT-IR analysis confirmed that grafting of L-lactide, under controlled condition, is possible to perform starting from the surface of functionalized MWCNTs. From differential scanning calorimetry results it was concluded that even low contents of chemically and irradiation functionalized MWCNTs had a significant effect on thermal properties of the prepared nanocomposites, raising the values of melting and glass transition temperatures. Thermogravimetric analysis (TGA) has shown that the degradation onset temperature for composites with chemically functionalized MWCNTs, was much higher than that for the neat poly(L-lactide) sample and composites with irradiation functionalized MWCNTs. Morphology studies by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) indicated that poly(L-lactide) covered surfaces and separated functionalized MWCNTs. Good dispersion of carbon nanotubes in polymer matrix enabled conductivity of synthesized materials, as determined by conductivity tests.


nanocomposites; carbon nanotube functionalization; poly(l-lactide); thermal properties

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Iijima S. Helical microtubules of graphitic carbon. Nature. 1991;354(6348):56-58.

Gupta TK, Kumar S. Fabrication of Carbon Nanotube/Polymer Nanocomposites. Carbon Nanotub Polym. January 2018:61-81.

Li H, Zare Y, Rhee KY. The percolation threshold for tensile strength of polymer/CNT nanocomposites assuming filler network and interphase regions. Mater Chem Phys. 2018;207:76-83.

Yoon JT, Lee SC, Jeong YG. Effects of grafted chain length on mechanical and electrical properties of nanocomposites containing polylactide-grafted carbon nanotubes. Compos Sci Technol. 2010;70(5):776-782.

Choudhary V, Gupt A. Polymer/Carbon Nanotube Nanocomposites. In: Carbon Nanotubes - Polymer Nanocomposites. InTech; 2011.

Xiefei Zhang, T. V. Sreekumar, Tao Liu A, Kumar S. Properties and Structure of Nitric Acid Oxidized Single Wall Carbon Nanotube Films. J Phys Chem B. 2004;108(42):16435–16440.

Liu, Rinzler, Dai, Hafner, Bradley, Boul, Lu, Iverson, Shelimov, Huffman, Rodriguez-Macias, Shon, Lee, Colbert, Smalley. Fullerene pipes. Science. 1998;280(5367):1253-6.

Kleut D, Jovanović S, Marković Z, Kepić D, Tošić D, Romčević N, Marinović-Cincović M, Dramićanin M, Holclajtner-Antunović I, Pavlović V, Dražić G, Milosavljević M, Todorović Marković B. Comparison of structural properties of pristine and gamma irradiated single-wall carbon nanotubes: Effects of medium and irradiation dose. Mater Charact. 2012;72:37-45.

Datsyuk V, Kalyva M, Papagelis K, Parthenios J, Tasis D, Siokou A, Kallitsis I, Galiotis C. Chemical oxidation of multiwalled carbon nanotubes. Carbon N Y. 2008;46(6):833-840.

Hamon MA, Chen J, Hu H, Chen Y, Itkis ME, Rao AM, Eklund PC, Haddon RC. Dissolution of Single-Walled Carbon Nanotubes. Adv Mater. 1999;11(10):834-840.

Chen J, Hamon MA, Hu H, Chen Y, Rao AM, Eklund PC, Haddon RC. Solution properties of single-walled carbon nanotubes. Science. 1998;282(5386):95-8.

Baek J-B, Lyons CB, Tan L-S. Grafting of Vapor-Grown Carbon Nanofibers via in-Situ Polycondensation of 3-Phenoxybenzoic Acid in Poly(phosphoric acid). Macromolecules. 2004;37(22):8278–8285.

Jin Z, Sun X, Xu G, Goh SH, Ji W. Nonlinear optical properties of some polymer/multi-walled carbon nanotube composites. Chem Phys Lett. 2000;318(6):505-510.

Riggs JE, Guo Z, Carroll DL, Sun Y-P. Strong Luminescence of Solubilized Carbon Nanotubes. J Am Chem Soc. 2000;122(24):5879-5880.

Lin Y, Zhou B, Shiral Fernando KA, Liu P, Allard LF, Sun Y-P. Polymeric Carbon Nanocomposites from Carbon Nanotubes Functionalized with Matrix Polymer. Macromolecules. 2003;36(19):7199-7204.

Yang M, Gao Y, Li H, Adronov A. Functionalization of multiwalled carbon nanotubes with polyamide 6 by anionic ring-opening polymerization. Carbon N Y. 2007;45(12):2327-2333.

Kong H, Luo P, Gao C, Yan D. Polyelectrolyte-functionalized multiwalled carbon nanotubes: preparation, characterization and layer-by-layer self-assembly. Polymer (Guildf). 2005;46(8):2472-2485.

Kong H, Li W, Gao C, Yan D, Jin Y, Walton DRM, Kroto HW. Poly(N-isopropylacrylamide)-Coated Carbon Nanotubes: Temperature-Sensitive Molecular Nanohybrids in Water. Macromolecules. 2004;37(18):6683–6686.

Qin S, Qin D, Ford WT, Herrera JE, Resasco Daniel E. Grafting of Poly(4-vinylpyridine) to Single-Walled Carbon Nanotubes and Assembly of Multilayer Films. Macromolecules. 2004;37(26):9963–9967.

Baskaran D, Mays JW, Bratcher MS. Polymer-Grafted Multiwalled Carbon Nanotubes through Surface-Initiated Polymerization. Angew Chemie Int Ed. 2004;43(16):2138-2142.

Seligra PG, Nuevo F, Lamanna M, Famá L. Covalent grafting of carbon nanotubes to PLA in order to improve compatibility. Compos Part B Eng. 2013;46:61-68.

Sun J, Shen J, Chen S, Cooper M, Fu H, Wu D, Yang Z, Sun J, Shen J, Chen S, Cooper MA, Fu H, Wu D, Yang Z. Nanofiller Reinforced Biodegradable PLA/PHA Composites: Current Status and Future Trends. Polymers (Basel). 2018;10(5):505.

Kaseem M, Hamad K, Deri F, Ko YG. A review on recent researches on polylactic acid/carbon nanotube composites. Polym Bull. 2017;74(7):2921-2937.

Seligra PG, Lamanna M, Famá L. Promising PLA-functionalized MWCNT composites to use in nanotechnology. Polym Compos. 2016;37(10):3066-3072.

Abozar Akbari, Mainak Majumder AT. Polylactic Acid (PLA) Carbon Nanotube Nanocomposites. In: Al. JKP et, ed. Handbook of Polymer Nanocomposites. Processing, Performance and Application – Volume B: Carbon Nanotube Based Polymer Composites. Springer-Verlag Berlin Heidelberg; 2015:283-297.

Gonçalves C, Gonçalves I, Magalhães F, Pinto A, Gonçalves C, Gonçalves IC, Magalhães FD, Pinto AM. Poly(lactic acid) Composites Containing Carbon-Based Nanomaterials: A Review. Polymers (Basel). 2017;9(12):269.

Kim H, Abdala AA, Macosko CW. Graphene/Polymer Nanocomposites. Macromolecules. 2010;43(16):6515-6530.

Brzeziński M, Biela T. Polylactide nanocomposites with functionalized carbon nanotubes and their stereocomplexes: A focused review. Mater Lett. 2014;121:244-250.

Jovanovic S, Markovic Z, Kleut D, Kepic D, Tosic D, Todorovic-Markovic B, Holclajtner-Antunovic I, Marinovic-Cincovic M. Covalent modification of single wall carbon nanotubes upon gamma irradiation in aqueous media. Hem Ind. 2011;65(5):479-487.

Marković VM, Eymery R, Yuan HC. A new approach of 60Co plant design for introduction of radiation sterilization in developing countries. Radiat Phys Chem. 1977;9(4-6):625-631.

Ke T, Sun X. Effects of Moisture Content and Heat Treatment on the Physical Properties of Starch and Poly(lactic acid) Blends. J Appl Polym Sci. 2001;81(12):3069-3082.

Blythe AR. Electrical resistivity measurements of polymer materials. Polym Test. 1984;4(2-4):195-209.

Qian Z, Wang C, Du G, Zhou J, Chen C, Ma J, Chen J, Feng H. Multicolour fluorescent graphene oxide by cutting carbon nanotubes upon oxidation. CrystEngComm. 2012;14(15):4976.

Bafandeh N, Larijani MM, Shafiekhani A, Hantehzadeh MR, Sheikh N. Effects of Contents of Multiwall Carbon Nanotubes in Polyaniline Films on Optical and Electrical Properties of Polyaniline. Chinese Phys Lett. 2016;33(11):117801.

Bhatia R, Kumar L. Functionalized carbon nanotube doping of P3HT:PCBM photovoltaic devices for enhancing short circuit current and efficiency. J Saudi Chem Soc. 2017;21(3):366-376.

Wepasnick KA, Smith BA, Bitter JL, Howard Fairbrother D. Chemical and structural characterization of carbon nanotube surfaces. Anal Bioanal Chem. 2010;396(3):1003-1014.

Ristić IS, Tanasić L, Nikolić LB, Cakić SM, Ilić OZ, Radičević RŽ, Budinski-Simendić JK. The Properties of Poly(l-Lactide) Prepared by Different Synthesis Procedure. J Polym Environ. 2011;19(2):419-430.

Xu H-S, Dai XJ, Lamb PR, Li Z-M. Poly(L-lactide) crystallization induced by multiwall carbon nanotubes at very low loading. J Polym Sci Part B Polym Phys. 2009;47(23):2341-2352.

Yoon JT, Jeong G, Lee SC, Min BG. Influences of poly(lactic acid)-grafted carbon nanotube on thermal, mechanical, and electrical properties of poly(lactic acid). Polym Adv Technol. 2009;20(7):631-638.


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