Implementing recyclable bio- and CO2-sourced synergetic dynamic matrices via precise control of curing and properties for natural fiber composites within industrially relevant resin transfer molding - 2025
Implementing recyclable bio- and CO2-sourced synergetic dynamic matrices via precise control of curing and properties for natural fiber composites within industrially relevant resin transfer molding
Seychal, Guillem; Campos, Bernard Miranda; Perli, Gabrielet al.
2025 • In Chemical Engineering Journal, 511, p. 161506
[en] The use of thermosets in natural fiber composites (NFC) presents major challenges related to their sustainability. Most alternatives struggle to meet industrial requirements relevant to conventional composite processing techniques. This study explores a synergetic copolymerization strategy that combines epoxy and CO2-derived polyhydroxyurethanes (PHU) to allow fine-tuned polymerization kinetics, including the suitability for the RTM process. We demonstrate a synergetic catalytic effect that accelerates curing compared to each neat component. The formulation maintains a low viscosity (<5 Pa.s) at room temperature while curing within 30 min at 80 °C, unattainable conditions with pure PHUs. Formulations suitable for resin transfer molding (RTM) were developed and demonstrated an improvement in mechanical performances compared to the homopolymer parents. RTM-made composite achieved a fiber volume fraction of 58-60% and a porosity below 1%, making them ideal for high-quality NFCs. The influence of hybridization content was investigated, and the influence of impregnation quality was highlighted while the PHU well-supported the adhesion quality. Moreover, the catalyst-free dynamic matrix allows the reshaping after curing, and flax fibers can be easily separated without toxic reagents from the polymeric matrix under mild conditions (60°C for 2 h) and reused, retaining properties similar to those of virgin yarns. This strategy could broaden the application of PHU chemistry in sustainable NFC manufacturing while preserving both natural and fossil feedstocks.
Research Center/Unit :
CESAM - Complex and Entangled Systems from Atoms to Materials - ULiège [BE] CERM - Center for Education and Research on Macromolecules - ULiège [BE]
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Seychal, Guillem ; University of the Basque Country - POLYMAT - Department of Polymers and Advanced Materials: Physics Chemistry and Technology - Donostia/SanSebastian - Spain ; University of Mons [UMons] - Center of Innovation and Research in Materials and Polymers [CIRMAP] - Laboratory of Polymeric and Composite Materials - Belgium
Campos, Bernard Miranda ; University of Lille - CNRS - Unité Matériaux et Transformations - France
Perli, Gabriel; University of the Basque Country - POLYMAT - Department of Polymers and Advanced Materials: Physics Chemistry and Technology - Donostia/SanSebastian - Spain
Placet, Vincent; Université Marie et Louis Pasteur - CNRS - Besançon - France
Grignard, Bruno ; University of Liège [ULiège] - Complex and Entangled Systems from Atoms to Materials [CESAM] Research Unit - Center for Education and Research on Macromolecules [CERM] - Belgium ; University of Liège [ULiège] - FRITCO2T Platform - Belgium
Bonnet, Fanny; University of Lille - CNRS - Unité Matériaux et Transformations - France
Detrembleur, Christophe ; University of Liège [ULiège] - Complex and Entangled Systems from Atoms to Materials [CESAM] Research Unit - Center for Education and Research on Macromolecules [CERM] - Belgium ; Walloon Excellence [ WEL] Research Institute - Wavre - Belgium
Sardon, Haritz; University of the Basque Country - POLYMAT - Department of Polymers and Advanced Materials: Physics Chemistry and Technology - Donostia/SanSebastian - Spain
Aranburu, Nora ; University of the Basque Country - POLYMAT - Department of Polymers and Advanced Materials: Physics Chemistry and Technology - Donostia/SanSebastian - Spain
Raquez, Jean-Marie; University of Mons [UMons] - Center of Innovation and Research in Materials and Polymers [CIRMAP] - Laboratory of Polymeric and Composite Materials - Belgium ; Walloon Excellence [ WEL] Research Institute - Wavre - Belgium
Language :
English
Title :
Implementing recyclable bio- and CO2-sourced synergetic dynamic matrices via precise control of curing and properties for natural fiber composites within industrially relevant resin transfer molding
Publication date :
May 2025
Journal title :
Chemical Engineering Journal
ISSN :
1385-8947
eISSN :
1873-3212
Publisher :
Elsevier B.V.
Volume :
511
Pages :
161506
Peer reviewed :
Peer Reviewed verified by ORBi
European Projects :
H2020 - 955700 - NIPU - SYNTHESIS, CHARACTERIZATION, STRUCTURE AND PROPERTIES OF NOVEL NONISOCYANATE POLYURETHANES
Funders :
F.R.S.-FNRS - Fund for Scientific Research Marie Skłodowska-Curie Actions CNRS - French National Centre for Scientific Research EU - European Union
Funding text :
The authors would like to thank the NIPU-EJD project for its financial support. This project received funding from the European Union's Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreements No 955700 and No 101154935. JMR and CD are F.R.S.-FNRS Research Directors and thank F.R.S.-FNRS, Belgium for funding. FB is CNRS research director and thanks the CNRS, France for funding. R\u00E9gion Hauts de France is acknowledged for funding the RTM from UMET.VP thanks EIPHI Graduate School, France (contract \u201CANR-17-EURE-0002\u201D) for its support.
Zhang, J., Lin, G., Vaidya, U., Wang, H., Past, present and future prospective of global carbon fibre composite developments and applications. Compos. Part B: Eng., 250, 2023, 110463, 10.1016/j.compositesb.2022.110463.
Baley, C., Bourmaud, A., Davies, P., Eighty years of composites reinforced by flax fibres: A historical review. Compos. Part A: Appl. Sci. Manuf., 144, 2021, 106333, 10.1016/j.compositesa.2021.106333.
Wazeer, A., Das, A., Abeykoon, C., Sinha, A., Karmakar, A., Composites for electric vehicles and automotive sector: A review. Green Energy Intell. Transp., 2022, 100043, 10.1016/j.geits.2022.100043.
Co, E.., JEC Observer: Current Trends in the Global Composites Industry 2021–2026. 2022, JEC Group.
Beiser, V., Why the World is Running Out of Sand. 2019, BBC.
Bourmaud, A., Beaugrand, J., Shah, D.U., Placet, V., Baley, C., Towards the design of high-performance plant fibre composites. Prog. Mater. Sci. 97 (2018), 347–408, 10.1016/j.pmatsci.2018.05.005.
Le Duigou, A., Davies, P., Baley, C., Environmental impact analysis of the production of flax fibres to be used as composite material reinforcement. J. Biobased Mater. Bioenergy 5:1 (2011), 153–165, 10.1166/jbmb.2011.1116.
Blanchard, J., Sobey, A., Comparative design of E-glass and flax structures based on reliability. Compos. Struct., 225, 2019, 111037, 10.1016/j.compstruct.2019.111037.
Andrew, J.J., Dhakal, H., Sustainable biobased composites for advanced applications: recent trends and future opportunities — A critical review. Compos. Part C: Open Access, 7, 2022, 100220, 10.1016/j.jcomc.2021.100220.
Zhang, J., Chevali, V.S., Wang, H., Wang, C.-H., Current status of carbon fibre and carbon fibre composites recycling. Compos. Part B: Eng., 193, 2020, 108053, 10.1016/j.compositesb.2020.108053.
Mohanty, A.K., Vivekanandhan, S., Pin, J.M., Misra, M., Composites from renewable and sustainable resources: Challenges and innovations. Science 362:6414 (2018), 536–542, 10.1126/science.aat9072.
Jeannin, T., Gabrion, X., Ramasso, E., Placet, V., About the fatigue endurance of unidirectional flax-epoxy composite laminates. Compos. Part B: Eng. 165 (2019), 690–701, 10.1016/j.compositesb.2019.02.009.
Witthayolankowit, K., Rakkijakan, T., Ayub, R., Kumaniaev, I., Pourchet, S., Boni, G., Watjanatepin, P., Zarafshani, H., Gabrion, X., Chevallier, A., Vo, N., Van Vuure, A., et al. Use of a fully biobased and non-reprotoxic epoxy polymer and woven hemp fabric to prepare environmentally friendly composite materials with excellent physical properties. Compos. Part B: Eng., 258, 2023, 110692, 10.1016/j.compositesb.2023.110692.
Lavaux, V., Lalevée, J., Epoxy curing in mild and eco-friendly conditions: Towards bisphenol A-free systems. Prog. Polym. Sci., 157, 2024, 101873, 10.1016/j.progpolymsci.2024.101873.
Asmatulu, E., Twomey, J., Overcash, M., Recycling of fiber-reinforced composites and direct structural composite recycling concept. J. Compos. Mater. 48:5 (2014), 593–608, 10.1177/0021998313476325.
Wu, X., Hartmann, P., Berne, D., De Bruyn, M., Cuminet, F., Wang, Z., Zechner, J.M., Boese, A.D., Placet, V., Caillol, S., Barta, K., Closed-loop recyclability of a biomass-derived epoxy-amine thermoset by methanolysis. Science, 384(6692), 2024, eadj9989, 10.1126/science.adj9989.
Clarke, R.W., Rognerud, E.G., Puente-Urbina, A., Barnes, D., Murdy, P., McGraw, M.L., Newkirk, J.M., Beach, R., Wrubel, J.A., Hamernik, L.J., Chism, K.A., Baer, A.L., et al. Manufacture and testing of biomass-derivable thermosets for wind blade recycling. Science 385:6711 (2024), 854–860, 10.1126/science.adp5395.
Zhao, X., Recycling of natural fiber composites: Challenges and opportunities. Resour. Conserv. Recycl., 2022, 25.
Chen, X., Dam, M.A., Ono, K., Mal, A., Shen, H., Nutt, S.R., Sheran, K., Wudl, F., A thermally re-mendable cross-linked polymeric material. Science 295:5560 (2002), 1698–1702, 10.1126/science.1065879.
Montarnal, D., Capelot, M., Tournilhac, F., Leibler, L., Silica-like malleable materials from permanent organic networks. Science 334:6058 (2011), 965–968, 10.1126/science.1212648.
Schenk, V., Labastie, K., Destarac, M., Olivier, P., Guerre, M., Vitrimer composites: current status and future challenges. Mater. Adv. 3:22 (2022), 8012–8029, 10.1039/D2MA00654E.
Schenk, V., De Calbiac, J., D'Elia, R., Olivier, P., Labastie, K., Destarac, M., Guerre, M., Epoxy vitrimer formulation for resin transfer molding: Reactivity, process, and material characterization. ACS Appl. Polym. Mater. 6:10 (2024), 6087–6095, 10.1021/acsapm.4c00796.
Ekuase, O.A., Anjum, N., Eze, V.O., Okoli, O.I., A review on the out-of-autoclave process for composite manufacturing. J. Compos. Sci., 6(6), 2022, 172, 10.3390/jcs6060172.
Schenk, V., D'Elia, R., Olivier, P., Labastie, K., Destarac, M., Guerre, M., Exploring the limits of high-Tg epoxy vitrimers produced through resin-transfer molding. ACS Appl. Mater. Interfaces 15:39 (2023), 46357–46367, 10.1021/acsami.3c10007.
Carré, C., Ecochard, Y., Caillol, S., Averous, L., From the synthesis of biobased cyclic carbonate to polyhydroxyurethanes: a promising route towards renewable NonIsocyanate Polyurethanes. ChemSusChem 12:15 (2019), 3410–3430, 10.1002/cssc.201900737.
Rehman, A., Saleem, F., Javed, F., Ikhlaq, A., Ahmad, S.W., Harvey, A., Recent advances in the synthesis of cyclic carbonates via CO2 cycloaddition to epoxides. J. Environ. Chem. Eng., 9(2), 2021, 105113, 10.1016/j.jece.2021.105113.
Seychal, G., Nickmilder, P., Lemaur, V., Ocando, C., Grignard, B., Leclère, P., Detrembleur, C., Lazzaroni, R., Sardon, H., Aranburu, N., Raquez, J.M., A novel approach to design structural natural fiber composites from sustainable CO 2 -derived polyhydroxyurethane thermosets with outstanding properties and circular features. Compos. Part A: Appl. Sci. Manuf., 185, 2024, 108311, 10.1016/j.compositesa.2024.108311.
Seychal, G., Ximenis, M., Lemaur, V., Grignard, B., Lazzaroni, R., Detrembleur, C., Sardon, H., Aranburu, N., Raquez, J.M., Synergetic hybridization strategy to enhance the dynamicity of poorly dynamic CO2 -derived vitrimers achieved by a simple copolymerization approach. Adv. Funct. Mater., 2024, 2412268, 10.1002/adfm.202412268.
Garipov, R.M., Sysoev, V.A., Mikheev, V.V., Zagidullin, A.I., Deberdeev, R.Y., Irzhak, V.I., Berlin, A.A., Reactivity of cyclocarbonate groups in modified epoxy–amine compositions. Dokl. Phys. Chem. 393:1–3 (2003), 289–292, 10.1023/B:DOPC.0000003463.07883.c9.
Cornille, A., Blain, M., Auvergne, R., Andrioletti, B., Boutevin, B., Caillol, S., A study of cyclic carbonate aminolysis at room temperature: effect of cyclic carbonate structures and solvents on polyhydroxyurethane synthesis. Polym. Chem. 8:3 (2017), 592–604, 10.1039/C6PY01854H.
Quienne, B., Poli, R., Pinaud, J., Caillol, S., Enhanced aminolysis of cyclic carbonates by beta-hydroxylamines for the production of fully biobased polyhydroxyurethanes. Green Chem. 23:4 (2021), 1678–1690, 10.1039/D0GC04120C.
Blain, M., Jean-Gérard, L., Auvergne, R., Benazet, D., Caillol, S., Andrioletti, B., Rational investigations in the ring opening of cyclic carbonates by amines. Green Chem. 16:9 (2014), 4286–4291, 10.1039/C4GC01032A.
Monie, F., Vidil, T., Grau, E., Grignard, B., Detrembleur, C., Cramail, H., The multifaceted role of water as an accelerator for the preparation of isocyanate-free polyurethane thermosets. Macromolecules, 2024, 10.1021/acs.macromol.4c01672.
Alves, M., Méreau, R., Grignard, B., Detrembleur, C., Jérôme, C., Tassaing, T., DFT investigation of the reaction mechanism for the guanidine catalysed ring-opening of cyclic carbonates by aromatic and alkyl-amines. RSC Adv. 7:31 (2017), 18993–19001, 10.1039/C7RA00220C.
Park, S.J., Seo, M.K., Lee, J.R., Lee, D.R., Studies on epoxy resins cured by cationic latent thermal catalysts: The effect of the catalysts on the thermal, rheological, and mechanical properties. J. Polym. Sci. Part A: Polym. Chem. 39:1 (2001), 187–195, 10.1002/1099-0518(20010101)39:1<187::AID-POLA210>3.0.CO;2-H.
Bourguignon, M., Grignard, B., Detrembleur, C., Cascade exotherms for rapidly producing hybrid nonisocyanate polyurethane foams from room temperature formulations. J. Am. Chem. Soc. 146:1 (2024), 988–1000, 10.1021/jacs.3c11637.
Gioia, C., Banella, M.B., Vannini, M., Celli, A., Colonna, M., Caretti, D., Resorcinol: A potentially bio-based building block for the preparation of sustainable polyesters. Eur. Polym. J. 73 (2015), 38–49, 10.1016/j.eurpolymj.2015.09.030.
Scodeller, I., Mansouri, S., Morvan, D., Muller, E., De Oliveira Vigier, K., Wischert, R., Jerome, F., Synthesis of renewable m-Xylylenediamine from biomass-derived furfural. Angew. Chem. 130:33 (2018), 10670–10674, 10.1002/ange.201803828.
Besse, V., Camara, F., Méchin, F., Fleury, E., Caillol, S., Pascault, J.P., Boutevin, B., How to explain low molar masses in PolyHydroxyUrethanes (PHUs). Eur. Polym. J. 71 (2015), 1–11, 10.1016/j.eurpolymj.2015.07.020.
Jaques, N.G., William De Lima Souza, J., Popp, M., Kolbe, J., Lia Fook, M.V., Ramos Wellen, R.M., Kinetic investigation of eggshell powders as biobased epoxy catalyzer. Compos. Part B: Eng., 183, 2020, 107651, 10.1016/j.compositesb.2019.107651.
Blain, M., Cornille, A., Boutevin, B., Auvergne, R., Benazet, D., Andrioletti, B., Caillol, S., Hydrogen bonds prevent obtaining high molar mass PHUs. J. Appl. Polym. Sci., 134(45), 2017, 44958, 10.1002/app.44958.
Cornille, A., Auvergne, R., Figovsky, O., Boutevin, B., Caillol, S., A perspective approach to sustainable routes for non-isocyanate polyurethanes. Eur. Polym. J. 87 (2017), 535–552, 10.1016/j.eurpolymj.2016.11.027.
Advani, S.G., Hsiao, K.T., 1 - Introduction to composites and manufacturing processes. Advani, S.G., Hsiao, K.T., (eds.) Manufacturing Techniques for Polymer Matrix Composites (PMCs), Elsevier Woodhead Publishing Series in Composites Science and Engineering, 2012, Woodhead Publishing, 1–12.
Rusnáková, S., Kalová, M., Jonšta, Z., Overview of production of pre-preg, prototype and testing. IOP Conf. Ser.: Mater. Sci. Eng., 448, 2018, 012069, 10.1088/1757-899x/448/1/012069.
Singh, D.K., Vaidya, A., Thomas, V., Theodore, M., Kore, S., Vaidya, U., Finite element modeling of the fiber-matrix interface in polymer composites. J. Compos. Sci., 4(2), 2020, 58, 10.3390/jcs4020058.
Potaufeux, J.E., Odent, J., Notta-Cuvier, D., Delille, R., Barrau, S., Giannelis, E.P., Lauro, F., Raquez, J.M., Mechanistic insights on ultra-tough polylactide-based ionic nanocomposites. Compos. Sci. Technol., 191, 2020, 108075, 10.1016/j.compscitech.2020.108075.
Kong, C., Park, H., Lee, J., Study on structural design and analysis of flax natural fiber composite tank manufactured by vacuum assisted resin transfer molding. Mater. Lett. 130 (2014), 21–25, 10.1016/j.matlet.2014.05.042.
Corbin, A.C., Soulat, D., Ferreira, M., Labanieh, A.R., Gabrion, X., Malécot, P., Placet, V., Towards hemp fabrics for high-performance composites: Influence of weave pattern and features. Compos. Part B: Eng., 181, 2020, 107582, 10.1016/j.compositesb.2019.107582.
Shah, D.U., Developing plant fibre composites for structural applications by optimising composite parameters: a critical review. J. Mater. Sci. 48:18 (2013), 6083–6107, 10.1007/s10853-013-7458-7.
Kersani, M., Lomov, S.V., Van Vuure, A.W., Bouabdallah, A., Verpoest, I., Damage in flax/epoxy quasi-unidirectional woven laminates under quasi-static tension. J. Compos. Mater. 49:4 (2015), 403–413, 10.1177/0021998313519282.
Ueki, Y., Lilholt, H., Madsen, B., Experimental evaluation of stiffness predictions of multiaxial flax fibre composites by classical laminate theory. PLOS ONE, 15(6), 2020, e0234701, 10.1371/journal.pone.0234701.
Ahrens, A., Bonde, A., Sun, H., Wittig, N.K., Hammershøj, H.C.D., Batista, G.M.F., Sommerfeldt, A., Frølich, S., Birkedal, H., Skrydstrup, T., Catalytic disconnection of C–O bonds in epoxy resins and composites. Nature 617:7962 (2023), 730–737, 10.1038/s41586-023-05944-6.
Sturgeon, M.R., Kim, S., Lawrence, K., Paton, R.S., Chmely, S.C., Nimlos, M., Foust, T.D., Beckham, G.T., A mechanistic investigation of acid-catalyzed cleavage of aryl-ether linkages: Implications for lignin depolymerization in acidic environments. ACS Sustain. Chem. Eng. 2:3 (2014), 472–485, 10.1021/sc400384w.
Das, M., Chacko, R., Varughese, S., An efficient method of recycling of CFRP waste using peracetic acid. ACS Sustain. Chem. Eng. 6:2 (2018), 1564–1571, 10.1021/acssuschemeng.7b01456.
Xing, M., Li, Z., Zheng, G., Du, Y., Chen, C., Wang, Y., Recycling of carbon fiber-reinforced epoxy resin composite via a novel acetic acid swelling technology. Compos. Part B: Eng., 224, 2021, 109230, 10.1016/j.compositesb.2021.109230.
Koolen, G., Soete, J., van Vuure, A.W., Interface modification and the influence on damage development of flax fibre — Epoxy composites when subjected to hygroscopic cycling. Mater. Today: Proc. 31 (2020), S273–S279, 10.1016/j.matpr.2020.01.183.
Yang, X., Berthold, F., Berglund, L.A., High-density molded cellulose fibers and transparent biocomposites based on oriented holocellulose. ACS Appl. Mater. Interfaces 11:10 (2019), 10310–10319, 10.1021/acsami.8b22134.
Malik, K., Ahmad, F., Yunus, N.A., Gunister, E., Nakato, T., Mouri, E., Ali, S., A review of flax fiber reinforced thermoset polymer composites: Thermal-physical properties, improvements and application. J. Nat. Fibers, 2021, 1–19, 10.1080/15440478.2021.1993507.
Hecker, M.D., Longana, M.L., Eloi, J.C., Thomsen, O., Hamerton, I., Recycling end-of-life sails by carbon fibre reclamation and composite remanufacture using the HiPerDiF fibre alignment technology. Compos. Part A: Appl. Sci. Manuf., 173, 2023, 107651, 10.1016/j.compositesa.2023.107651.
