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Development of enhanced co-continuous PVDF/PET nanocomposites via synergistic effects of graphite particle size, hybrid systems, and reduced graphene oxide

  • Sahar Shojaei , Ehsan Rostami-Tapeh-Esmaeil , Frej Mighri EMAIL logo , Saïd Elkoun , Martin Brassard , Elaheh Oliaii , Philippe Pelletier , Guy Jourdain and Yves Bonnefoy
Published/Copyright: March 24, 2025
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International Polymer Processing
From the journal International Polymer Processing Volume 40 Issue 2

Abstract

This study explores the development of electrically conductive co-continuous polyvinylidene fluoride/polyethylene terephthalate (PVDF/PET) nanocomposites incorporating graphite (GR) and reduced graphene oxide (rGO) for potential use in proton exchange membrane fuel cell (PEMFC) bipolar plates. The influence of GR particle size, concentration (20–60 wt%), and hybrid GR/GR and GR/GR/rGO combinations on electrical, thermal, mechanical, and water absorption properties was systematically investigated. Scanning electron microscopy revealed GR localization within the PET phase and the formation of a dense conductive network. The optimal composition, a hybrid G2/G3 (45/15 wt%) system, achieved low through-plane (0.93 Ω cm) and in-plane (0.71 Ω cm) resistivities, further reduced with 2 wt% rGO (0.89 Ω cm through-plane and 0.62 Ω cm in-plane). This formulation also exhibited superior thermal stability (onset degradation at ∼490 °C) and mechanical properties, with a flexural strength of 44.4 MPa and modulus of 16.4 GPa. Additionally, water absorption decreased significantly to 0.05 %. These findings demonstrate the potential of hybrid GR/rGO nanocomposites for enhanced durability and performance in PEMFC applications, offering a balance between electrical conductivity, mechanical strength, and environmental resilience.

Keywords: co-continuous morphology; bipolar plate; proton exchange membrane fuel cell; electrically conductive nanocomposites; graphite
Corresponding author: Frej Mighri, Research Center for High Performance Polymer and Composite Systems, CREPEC, Montreal, Canada; and Department of Chemical Engineering, Laval University, Quebec, G1A 0A6, Canada, E-mail:

  1. Research ethics: Not applicable.

  2. Informed consent: Not applicable.

  3. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  4. Use of Large Language Models, AI and Machine Learning Tools: None declared.

  5. Conflict of interest: The authors declare no conflicts of interest regarding this article.

  6. Research funding: Main funding was received from the Natural Sciences and Engineering Research Council of Canada (NSERC) and PRIMA Quebec.

  7. Data availability: All data generated or analyzed during this study are available from the corresponding author upon request.

References

Afsharhashemkhani, S., Jamal-Omidi, M., and Tavakolian, M. (2022). A molecular dynamics study on the mechanical properties of defective CNT/epoxy nanocomposites using static and dynamic deformation approaches. Int. Polym. Process. 37: 176–190, https://doi.org/10.1515/ipp-2021-4182.Search in Google Scholar

Alhulaybi, Z. and Dubdub, I. (2023). Comprehensive kinetic study of PET pyrolysis using TGA. Polymers 15: 3010–3023, https://doi.org/10.3390/polym15143010.Search in Google Scholar PubMed PubMed Central

Alo, O., Otunniyi, I., and Pienaar, H. (2019). Prospects of graphite-polypropylene/epoxy blend composite for high performance bipolar plate in polymer electrolyte membrane fuel cell. IOP Conf. Ser.: Mater. Sci. Eng. 655: 012035, https://doi.org/10.1088/1757-899X/655/1/012035.Search in Google Scholar

Alo, O.A., Otunniyi, I.O., and Pienaar, H. (2020). Development of graphite‐filled polymer blends for application in bipolar plates. Polym. Compos. 41: 3364–3375, https://doi.org/10.1002/pc.25625.Search in Google Scholar

Asgharzadeh, H. and Eslami, S. (2019). Effect of reduced graphene oxide nanoplatelets content on the mechanical and electrical properties of copper matrix composite. J. Alloys Compd. 806: 553–565, https://doi.org/10.1016/j.jallcom.2019.07.183.Search in Google Scholar

Athmouni, N., Mighri, F., and Elkoun, S. (2016). Effect of unfunctionalized and HNO3‐functionalized MWCNT on the mechanical and electrical performances of PEMFC bipolar plates. J. Appl. Polym. Sci. 133: 43624, https://doi.org/10.1002/app.43624.Search in Google Scholar

Athmouni, N., Mighri, F., and Elkoun, S. (2018). Surface modification of multiwall carbon nanotubes and its effect on mechanical and through‐plane electrical resistivity of PEMFC bipolar plate nanocomposites. Polym. Adv. Technol. 29: 294–301, https://doi.org/10.1002/pat.4294.Search in Google Scholar

Barretta, R., Faghidian, S.A., and Marotti de Sciarra, F. (2020). A consistent variational formulation of Bishop nonlocal rods. Cont. Mech. Thermodyn. 32: 1311–1323, https://doi.org/10.1007/s00161-019-00843-6.Search in Google Scholar

Behera, K., Yadav, M., Chiu, F.-C., and Rhee, K.Y. (2019). Graphene nanoplatelet-reinforced poly (vinylidene fluoride)/high density polyethylene blend-based nanocomposites with enhanced thermal and electrical properties. Nanomaterials 9: 1364–1397, https://doi.org/10.3390/nano9030361.Search in Google Scholar PubMed PubMed Central

Boyaci San, F.G. and Tekin, G. (2013). A review of thermoplastic composites for bipolar plate applications. Int. J. Energy Res. 37: 283–309, https://doi.org/10.1002/er.3005.Search in Google Scholar

Chunhui, S., Mu, P., and Runzhang, Y. (2008). The effect of particle size gradation of conductive fillers on the conductivity and the flexural strength of composite bipolar plate. Int. J. Hydrogen Energy 33: 1035–1039, https://doi.org/10.1016/j.ijhydene.2007.11.013.Search in Google Scholar

Dallaev, R., Pisarenko, T., Sobola, D., Orudzhev, F., Ramazanov, S., and Trčka, T. (2022). Brief review of PVDF properties and applications potential. Polymers 14: 4793, https://doi.org/10.3390/polym14224793.Search in Google Scholar PubMed PubMed Central

de Jesus Silva, A.J., Contreras, M.M., Nascimento, C.R., and da Costa, M.F. (2020). Kinetics of thermal degradation and lifetime study of poly (vinylidene fluoride) (PVDF) subjected to bioethanol fuel accelerated aging. Heliyon 6: e04573, https://doi.org/10.1016/j.heliyon.2020.e04573.Search in Google Scholar PubMed PubMed Central

Dhakate, S., Sharma, S., Borah, M., Mathur, R., and Dhami, T. (2008). Development and characterization of expanded graphite-based nanocomposite as bipolar plate for polymer electrolyte membrane fuel cells (PEMFCs). Energy fuel. 22: 3329–3334, https://doi.org/10.1021/ef800135f.Search in Google Scholar

Ezat, G.S., Kelly, A.L., Youseffi, M., and Coates, P.D. (2022). Tensile, rheological, and morphological characterizations of multi-walled carbon nanotube/polypropylene composites prepared by microinjection and compression molding. Int. Polym. Process. 37: 45–53, https://doi.org/10.1515/ipp-2021-4156.Search in Google Scholar

Fina, A., Han, Z., Saracco, G., Gross, U., and Mainil, M. (2012). Morphology and conduction properties of graphite‐filled immiscible PVDF/PPgMA blends. Polym. Adv. Technol. 23: 1572–1579, https://doi.org/10.1002/pat.3031.Search in Google Scholar

Ghanbari, A., Heuzey, M.-C., and Carreau, P. (2021). The effect of nanosilicates on the performance of polyethylene terephthalate films prepared by twin-screw extrusion. Int. Polym. Process. 36: 358–366, https://doi.org/10.1515/ipp-2020-4044.Search in Google Scholar

Gregorio, R. and Ueno, E. (1999). Effect of crystalline phase, orientation and temperature on the dielectric properties of poly (vinylidene fluoride) (PVDF). J. Mater. Sci. 34: 4489–4500, https://doi.org/10.1023/A:1004689205706.10.1023/A:1004689205706Search in Google Scholar

Heo, S., Yun, J., Oh, K., and Han, K. (2006). Influence of particle size and shape on electrical and mechanical properties of graphite reinforced conductive polymer composites for the bipolar plate of PEM fuel cells. Adv. Compos. Mater. 15: 115–126, https://doi.org/10.1163/156855106776829356.Search in Google Scholar

Hidayah, N., Liu, W.-W., Lai, C.-W., Noriman, N., Khe, C.-S., Hashim, U., and Lee, H.C. (2017). Comparison on graphite, graphene oxide and reduced graphene oxide: synthesis and characterization. AIP Conf. Proc. 1892: 150002, https://doi.org/10.1063/1.5005764.Search in Google Scholar

Hui, C., Hong-Bo, L., Li, Y., and Jian-Xin, L. (2010). Study on the preparation and properties of novolac epoxy/graphite composite bipolar plate for PEMFC. Int. J. Hydrogen Energy 35: 3105–3109, https://doi.org/10.1016/j.ijhydene.2009.08.030.Search in Google Scholar

Ji, L.N. (2013). Study on preparation process and properties of polyethylene terephthalate (PET). Appl. Mech. Mater. 312: 406–410, https://doi.org/10.4028/www.scientific.net/AMM.312.406.Search in Google Scholar

Jiang, R., Lashkari, P., Zhou, S., and Hrymak, A.N. (2022). Effect of mixing conditions and polymer particle size on the properties of polypropylene/graphite nanoplatelets micromoldings. Int. Polym. Process. 37: 372–382, https://doi.org/10.1515/ipp-2022-0004.Search in Google Scholar

Kim, H., Abdala, A.A., and Macosko, C.W. (2010). Graphene/polymer nanocomposites. Macromolecules 43: 6515–6530, https://doi.org/10.1021/ma100572e.Search in Google Scholar

Kim, M., Lim, J.W., Kim, K.H., and Lee, D.G. (2013). Bipolar plates made of carbon fabric/phenolic composite reinforced with carbon black for PEMFC. Compos. Struct. 96: 569–575, https://doi.org/10.1016/j.compstruct.2012.09.017.Search in Google Scholar

Kuan, H.-C., Ma, C.-C.M., Chen, K.H., and Chen, S.-M. (2004). Preparation, electrical, mechanical and thermal properties of composite bipolar plate for a fuel cell. J. Power Sources 134: 7–17, https://doi.org/10.1016/j.jpowsour.2004.02.024.Search in Google Scholar

Lavin-Lopez, M.d. P., Romero, A., Garrido, J., Sanchez-Silva, L., and Valverde, J.L. (2016). Influence of different improved Hummers method modifications on the characteristics of graphite oxide in order to make a more easily scalable method. Ind. Eng. Chem. Res. 55: 12836–12847, https://doi.org/10.1021/acs.iecr.6b03533.Search in Google Scholar

Lee, A.-Y., Chong, M.-H., Park, M., Kim, H.-Y., and Park, S.-J. (2014). Effect of chemically reduced graphene oxide on epoxy nanocomposites for flexural behaviors. Carbon Lett 15: 67–70, https://doi.org/10.5714/CL.2014.15.1.067.Search in Google Scholar

Lee, J.H., Jang, Y.K., Hong, C.E., Kim, N.H., Li, P., and Lee, H.K. (2009). Effect of carbon fillers on properties of polymer composite bipolar plates of fuel cells. J. Power Sources 193: 523–529, https://doi.org/10.1016/j.jpowsour.2009.04.029.Search in Google Scholar

Li, X., Huang, K., Wang, X., Li, H., Shen, W., Zhou, X., Xu, J., and Wang, X. (2018). Effect of montmorillonite on morphology, rheology, and properties of a poly [styrene–(ethylene-co-butylene)–styrene]/poly (ɛ-caprolactone) nanocomposite. J. Mater. Sci. 53: 1191–1203, https://doi.org/10.1007/s10853-017-1606-4.Search in Google Scholar

López Gaxiola, D., Jubinski, M.M., Keith, J.M., King, J.A., and Miskioglu, I. (2010). Effects of carbon fillers on tensile and flexural properties in polypropylene‐based resins. J. Appl. Polym. Sci. 118: 1620–1633, https://doi.org/10.1002/app.32540.Search in Google Scholar

Mehmood, Z., Shah, S.A.A., Omer, S., Idrees, R., and Saeed, S. (2024). Scalable synthesis of high-quality, reduced graphene oxide with a large C/O ratio and its dispersion in a chemically modified polyimide matrix for electromagnetic interference shielding applications. RSC Adv. 14: 7641–7654, https://doi.org/10.1039/D4RA00329B.Search in Google Scholar PubMed PubMed Central

Mikhailenko, S., Guiver, M., and Kaliaguine, S. (2008). Measurements of PEM conductivity by impedance spectroscopy. Solid State Ionics 179: 619–624, https://doi.org/10.1016/j.ssi.2008.04.020.Search in Google Scholar

Nguyen, L., Mighri, F., Deyrail, Y., and Elkoun, S. (2010). Conductive materials for proton exchange membrane fuel cell bipolar plates made from PVDF, PET and co‐continuous PVDF/PET filled with carbon additives. Fuel Cells 10: 938–948, https://doi.org/10.1002/fuce.200900171.Search in Google Scholar

Park, W., Hu, J., Jauregui, L.A., Ruan, X., and Chen, Y.P. (2014). Electrical and thermal conductivities of reduced graphene oxide/polystyrene composites. Appl. Phys. Lett. 104: 113101, https://doi.org/10.1063/1.4869026.Search in Google Scholar

Phuangngamphan, M., Okhawilai, M., Hiziroglu, S., and Rimdusit, S. (2019). Development of highly conductive graphite‐/graphene‐filled polybenzoxazine composites for bipolar plates in fuel cells. J. Appl. Polym. Sci. 136: 47183, https://doi.org/10.1002/app.47183.Search in Google Scholar

Planes, E., Flandin, L., and Alberola, N. (2012). Polymer composites bipolar plates for PEMFCs. Energy Proc. 20: 311–323, https://doi.org/10.1016/j.egypro.2012.03.031.Search in Google Scholar

Rao, S., Upadhyay, J., Polychronopoulou, K., Umer, R., and Das, R. (2018). Reduced graphene oxide: effect of reduction on electrical conductivity. J. Compos. Sci. 2: 25, https://doi.org/10.3390/jcs2020025.Search in Google Scholar

Rosli, R., Sulong, A., Daud, W., Zulkifley, M., Husaini, T., Rosli, M., Majlan, E., and Haque, M. (2017). A review of high-temperature proton exchange membrane fuel cell (HT-PEMFC) system. Int. J. Hydrogen Energy 42: 9293–9314, https://doi.org/10.1016/j.ijhydene.2016.06.211.Search in Google Scholar

Saxena, P. and Shukla, P. (2021). A comprehensive review on fundamental properties and applications of poly (vinylidene fluoride) (PVDF). Adv. Compos. Hybrid Mater. 4: 8–26, https://doi.org/10.1007/s42114-021-00217-0.Search in Google Scholar

Shen, C., Pan, M., Hua, Z., and Yuan, R. (2007). Aluminate cement/graphite conductive composite bipolar plate for proton exchange membrane fuel cells. J. Power Sources 166: 419–423, https://doi.org/10.1016/j.jpowsour.2007.01.082.Search in Google Scholar

Shojaei, S., Rostami‐Tapeh‐Esmaeil, E., and Mighri, F. (2024). A review on key factors influencing the electrical conductivity of proton exchange membrane fuel cell composite bipolar plates. Polym. Adv. Technol. 35: e6301, https://doi.org/10.1002/pat.6301.Search in Google Scholar

Shojaie, S., Vahidifar, A., Naderi, G., Shokri, E., Mekonnen, T.H., and Esmizadeh, E. (2021). Physical hybrid of nanographene/carbon nanotubes as reinforcing agents of NR-based rubber foam. Polymers 13: 2346, https://doi.org/10.3390/polym13142346.Search in Google Scholar PubMed PubMed Central

Singh, A.K., Bedi, R., and Kaith, B.S. (2021). Composite materials based on recycled polyethylene terephthalate and their properties–A comprehensive review. Compos. Part B Eng. 219: 108928, https://doi.org/10.1016/j.compositesb.2021.108928.Search in Google Scholar

Song, J., Mighri, F., Ajji, A., and Lu, C. (2012). Polyvinylidene fluoride/poly (ethylene terephthalate) conductive composites for proton exchange membrane fuel cell bipolar plates: crystallization, structure, and through‐plane electrical resistivity. Polym. Eng. Sci. 52: 2552–2558, https://doi.org/10.1002/pen.23216.Search in Google Scholar

Strankowski, M., Włodarczyk, D., Piszczyk, Ł., and Strankowska, J. (2016). Polyurethane nanocomposites containing reduced graphene oxide, FTIR, Raman, and XRD studies. J. Spectrosc. 2016: 7520741, https://doi.org/10.1155/2016/7520741.Search in Google Scholar

Taha, M., Hassan, M., Essa, S., and Tartor, Y. (2013). Use of Fourier transform infrared spectroscopy (FTIR) for rapid and accurate identification of yeasts isolated from humans and animals. Int. J. Vet. Sci. Med. 1: 15–20, https://doi.org/10.1016/j.ijvsm.2013.03.001.Search in Google Scholar

Tarannum, F., Danayat, S., Nayal, A., Muthaiah, R., Annam, R.S., and Garg, J. (2023). Thermally expanded graphite polyetherimide composite with superior electrical and thermal conductivity. Mater. Chem. Phys. 298: 127404, https://doi.org/10.1016/j.matchemphys.2023.127404.Search in Google Scholar

Wang, H., Wang, A., Yin, H., Ding, Y., and Li, C. (2024). Convenient preparation of expanded graphite and graphite nanosheets as well as improvement of electrical conductivity of polyurethane by filling graphite nanosheets. Mater. Sci. Eng. B 300: 117061, https://doi.org/10.1016/j.mseb.2023.117061.Search in Google Scholar

Witpathomwong, S., Okhawilai, M., Jubsilp, C., Karagiannidis, P., and Rimdusit, S. (2020). Highly filled graphite/graphene/carbon nanotube in polybenzoxazine composites for bipolar plate in PEMFC. Int. J. Hydrogen Energy 45: 30898–30910, https://doi.org/10.1016/j.ijhydene.2020.08.006.Search in Google Scholar

Wu, J., Yuan, X.Z., Martin, J.J., Wang, H., Zhang, J., Shen, J., Wu, S., and Merida, W. (2008). A review of PEM fuel cell durability: degradation mechanisms and mitigation strategies. J. Power Sources 184: 104–119, https://doi.org/10.1016/j.jpowsour.2008.06.006.Search in Google Scholar

Wu, M. and Shaw, L.L. (2005). A novel concept of carbon-filled polymer blends for applications in PEM fuel cell bipolar plates. Int. J. Hydrogen Energy 30: 373–380, https://doi.org/10.1016/j.ijhydene.2004.08.005.Search in Google Scholar

Xu, C., Shi, X., Ji, A., Shi, L., Zhou, C., and Cui, Y. (2015). Fabrication and characteristics of reduced graphene oxide produced with different green reductants. PLoS One 10: e0144842, https://doi.org/10.1371/journal.pone.0144842.Search in Google Scholar PubMed PubMed Central

Yoo, H.J., Mahapatra, S.S., and Cho, J.W. (2014). High-speed actuation and mechanical properties of graphene-incorporated shape memory polyurethane nanofibers. J. Phys. Chem. C 118: 10408–10415, https://doi.org/10.1021/jp500709m.Search in Google Scholar

Zaaba, N., Foo, K., Hashim, U., Tan, S., Liu, W.-W., and Voon, C. (2017). Synthesis of graphene oxide using modified Hummers method: solvent influence. Procedia Eng. 184: 469–477, https://doi.org/10.1016/j.proeng.2017.04.118.Search in Google Scholar

Zhang, S., Ukrainczyk, N., Zaoui, A., and Koenders, E. (2024). Electrical conductivity of geopolymer-graphite composites: percolation, mesostructure and analytical modeling. Constr. Build. Mater. 411: 134536, https://doi.org/10.1016/j.conbuildmat.2023.134536.Search in Google Scholar

Zhao, X., Wang, H., Fu, Z., and Li, Y. (2018). Enhanced interfacial adhesion by reactive carbon nanotubes: new route to high-performance immiscible polymer blend nanocomposites with simultaneously enhanced toughness, tensile strength, and electrical conductivity. ACS Appl. Mater. Interfaces 10: 8411–8416, https://doi.org/10.1021/acsami.7b19455.Search in Google Scholar PubMed PubMed Central

Received: 2024-12-14
Accepted: 2025-02-07
Published Online: 2025-03-24
Published in Print: 2025-05-26

© 2025 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Review Article
  3. Corrosion resistive conducting polymeric nanocomposite-based coatings on steel: a mechanistic insight
  4. Research Articles
  5. Effect of compatibilizer type on the properties of thermoplastic elastomers based on recycled polyethylene at high ground tire rubber content
  6. Analyzing the effects of solid fraction and heat treatment on the mechanical properties of 3D printed polymer lattices
  7. Effect of polyvinyl acetate on the properties of biodegradable thermoplastic starch/polyethylene glycol blends
  8. A color masterbatch assistance system for optimizing product color by masterbatch addition in injection molding of post-industrial recyclates
  9. Enhancing 3D printing with composite filaments incorporating electronic waste: a study on flexural and compression strength
  10. Development of enhanced co-continuous PVDF/PET nanocomposites via synergistic effects of graphite particle size, hybrid systems, and reduced graphene oxide
  11. Integration of nanographene and action of fiber sequences on functional behaviour of composite laminates
  12. Effect of chain branching on the rheological properties of HDPE/LLDPE and HDPE/LDPE blends under shear and elongational flows and evaluation of die swell and flow instabilities
  13. Effect of graphene nanoplatelets (GnPs) on low velocity impact properties of hybrid kevlar/basalt fiber reinforced epoxy based composites
  14. Sustainability in rotational molding: a study on recycling and the influence of additives
https://doi.org/10.1515/ipp-2024-0173
Keywords for this article
co-continuous morphology; bipolar plate; proton exchange membrane fuel cell; electrically conductive nanocomposites; graphite

Articles in the same Issue

  1. Frontmatter
  2. Review Article
  3. Corrosion resistive conducting polymeric nanocomposite-based coatings on steel: a mechanistic insight
  4. Research Articles
  5. Effect of compatibilizer type on the properties of thermoplastic elastomers based on recycled polyethylene at high ground tire rubber content
  6. Analyzing the effects of solid fraction and heat treatment on the mechanical properties of 3D printed polymer lattices
  7. Effect of polyvinyl acetate on the properties of biodegradable thermoplastic starch/polyethylene glycol blends
  8. A color masterbatch assistance system for optimizing product color by masterbatch addition in injection molding of post-industrial recyclates
  9. Enhancing 3D printing with composite filaments incorporating electronic waste: a study on flexural and compression strength
  10. Development of enhanced co-continuous PVDF/PET nanocomposites via synergistic effects of graphite particle size, hybrid systems, and reduced graphene oxide
  11. Integration of nanographene and action of fiber sequences on functional behaviour of composite laminates
  12. Effect of chain branching on the rheological properties of HDPE/LLDPE and HDPE/LDPE blends under shear and elongational flows and evaluation of die swell and flow instabilities
  13. Effect of graphene nanoplatelets (GnPs) on low velocity impact properties of hybrid kevlar/basalt fiber reinforced epoxy based composites
  14. Sustainability in rotational molding: a study on recycling and the influence of additives
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