Reactive melt crosslinking of cellulose nanocrystals/poly (ε-caprolactone) for heat-shrinkable network
Open accessAbstract
Focusing on the challenge of non-biodegradable plastics replacement, we propose a design for peroxide-initiated crosslinking of biodegradable poly(ε-caprolactone) (PCL) and renewable cellulose nanocrystals (CNCs) bionanocomposites. An industrially scalable water-assisted reactive melt-processing (REx) is studied to explore the hypothesis of synergy between simultaneous effects of water on improving CNC dispersion and boosting PCL branching/crosslinking. We demonstrate that the melt processing control enables the preparation of targeted thermoplastic/thermoset bionanocomposites with gel content up to ≈ 40 %, identified as the limit of their melt-processability. Structural characterization reveals that ≈ 70 wt% of the initial CNC content is irreversibly incorporated in a percolating network, enhancing the crosslinked bionanocomposites properties. The bionanocomposites' complex viscosity and elastic character increase with the gel content, thus improving PCL melt performance. Furthermore, the irreversible entrapment of CNCs in the 3D percolating network provides heat-shrinkability, indicating a potential of the reacted bionanocomposites for heat-triggered shape-memory.
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Melt blending offers scalability and solvent-free processing, but achieving uniform NC dispersion in PCL remains a challenge due to the hydrophilic nature of NC and its tendency to agglomerate within the hydrophobic PCL matrix.
“Melt blending offers the advantage of scalability and solvent-free processing, although achieving uniform NC dispersion remains a challenge due to its hydrophilic nature and tendency to agglomerate within the hydrophobic PCL matrix [21,66]”
From Nanocellulose-Reinforced Poly(Lactic Acid) and Poly(ε-caprolactone) Bio-Nanocomposites: A Review and Future Outlook for Poly(Lactic Acid)/Poly(ε-caprolactone) Blend Systems (2025) · cites this paper as [66]
The Introduction says CNC surface hydroxyl groups promote agglomeration and describes wet-feeding as easier to scale up; the Melt rheology section reports CNC aggregation and poor adhesion after traditional melt processing. However, the paper uses a water-assisted process rather than establishing the claimed solvent-free advantage, and it does not explicitly attribute the dispersion problem to hydrophilic CNCs in a hydrophobic PCL matrix. (LLM, conf=0.83)
Experimental — accuracy not yet measuredTreated CNCs improve interfacial adhesion and dispersion within PCL, resulting in enhanced mechanical performance compared to unmodified fillers.
“Avella et al. [66] demonstrated that treated CNCs improved interfacial adhesion and dispersion within PCL, resulting in enhanced mechanical performance compared to unmodified fillers.”
From Nanocellulose-Reinforced Poly(Lactic Acid) and Poly(ε-caprolactone) Bio-Nanocomposites: A Review and Future Outlook for Poly(Lactic Acid)/Poly(ε-caprolactone) Blend Systems (2025) · cites this paper as [66]
Section 3.5 reports better CNC dispersion in the crosslinked PCL composite than in the unreacted composite, along with stronger network reinforcement and more efficient stress transfer. It also reports increased storage modulus, but reduced deformability. The paper studies reactive crosslinking of the composite, rather than showing that separately treated CNC fillers generally improve mechanical performance over unmodified fillers. (LLM, conf=0.83)
Experimental — accuracy not yet measuredNC can enhance the thermal stability and crystallinity of PCL composites, although this effect is strongly dependent on the type of NC and its dispersion quality.
“TGA and DSC analyses from multiple studies indicate that NC can enhance the thermal stability and crystallinity of PCL composites, although this effect is strongly dependent on the type of NC and its dispersion quality [22,66,67,68]”
From Nanocellulose-Reinforced Poly(Lactic Acid) and Poly(ε-caprolactone) Bio-Nanocomposites: A Review and Future Outlook for Poly(Lactic Acid)/Poly(ε-caprolactone) Blend Systems (2025) · cites this paper as [66]
Section 3.5 (page not available) reports greater crystallinity in crosslinked PCL–CNC than in its crosslinked PCL reference, but lower overall crystallinity in the unreacted PCL–CNC composite. It also links improved CNC dispersion to delayed degradation, while the reported shift to a higher degradation temperature is for CNC, not PCL. The paper studies CNCs, not different types of nanocellulose, so it does not establish dependence on NC type. (LLM, conf=0.86)
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Cites
Production, use, and fate of all plastics ever made
Geyer, R., Jambeck, J. R., & Law, K. L. (2017) · Science Advances · doi:10.1126/sciadv.1700782 · Cited by 18,606 · see citing works
Review of progress in shape-memory polymers
Liu, C., Qin, H., & Mather, P. T. (2007) · Journal of Materials Chemistry · doi:10.1039/b615954k · Cited by 1,942 · see citing works
Currie, L. A. (1995) · Pure and Applied Chemistry · doi:10.1351/pac199567101699 · Cited by 1,716 · see citing works
Developing fibrillated cellulose as a sustainable technological material
Li, T., Chen, C., Brozena, A. H., Zhu, J. Y., Xu, L., Driemeier, C., Dai, J., Rojas, O. J., Isogai, A., Wågberg, L., et al. (2021) · Nature · doi:10.1038/s41586-020-03167-7 · Cited by 1,674 · see citing works
Cellulose nanocrystals reinforced poly(oxyethylene)
Azizi Samir, M. A. S., Alloin, F., Sanchez, J.-Y., & Dufresne, A. (2004) · Polymer · doi:10.1016/j.polymer.2004.03.094 · Cited by 398 · see citing works
Van Gurp-Palmen-plot: a way to characterize polydispersity of linear polymers
Trinkle, S., & Friedrich, C. (2001) · Rheologica Acta · doi:10.1007/s003970000137 · Cited by 393 · see citing works
An investigation of chemical crosslinking effect on properties of high-density polyethylene
Khonakdar, H. A., Morshedian, J., Wagenknecht, U., & Jafari, S. H. (2003) · Polymer · doi:10.1016/s0032-3861(03)00363-x · Cited by 375 · see citing works
Hose — a novel substructure code
Bremser, W. (1978) · Analytica Chimica Acta · doi:10.1016/s0003-2670(01)83100-7 · Cited by 325 · see citing works
Kono, H., Yunoki, S., Shikano, T., Fujiwara, M., Erata, T., & Takai, M. (2002) · Journal of the American Chemical Society · doi:10.1021/ja010704o · Cited by 297 · see citing works
Recent Advances in Reactive Extrusion Processing of Biodegradable Polymer‐Based Compositions
Raquez, J., Narayan, R., & Dúbois, P. (2008) · Macromolecular Materials and Engineering · doi:10.1002/mame.200700395 · Cited by 251 · see citing works
Self-citationSurface Engineering of Ultrafine Cellulose Nanofibrils toward Polymer Nanocomposite Materials
Fujisawa, S., Saito, T., Kimura, S., Iwata, T., & Isogai, A. (2013) · Biomacromolecules · doi:10.1021/bm400178m · Cited by 185 · see citing works
Wei, L., McDonald, A. G., & Stark, N. M. (2015) · Biomacromolecules · doi:10.1021/acs.biomac.5b00049 · Cited by 170 · see citing works
Imre, B., García, L., Puglia, D., & Vilaplana, F. (2018) · Carbohydrate Polymers · doi:10.1016/j.carbpol.2018.12.082 · Cited by 156 · see citing works
Thermally recyclable polylactic acid/cellulose nanocrystal films through reactive extrusion process
Dhar, P., Tarafder, D., Kumar, A., & Katiyar, V. (2016) · Polymer · doi:10.1016/j.polymer.2016.02.004 · Cited by 149 · see citing works
Wei, L., Stark, N. M., & McDonald, A. G. (2015) · Green Chemistry · doi:10.1039/c5gc01568e · Cited by 124 · see citing works
Morphology, Crystallinity, and Molecular Weight of Poly(ε-caprolactone)/Graphene Oxide Hybrids
Castilla-Cortázar, I., Vidaurre, A., Marí, B., & Campillo-Fernández, A. J. (2019) · Polymers · doi:10.3390/polym11071099 · Cited by 86 · see citing works
Dynamics in Crystallites of Poly(ε-caprolactone) As Investigated by Solid-State NMR
Schäler, K., Achilles, A., Bärenwald, R., Hackel, C., & Saalwächter, K. (2013) · Macromolecules · doi:10.1021/ma401532v · Cited by 71 · see citing works
Sakakibara, K., Moriki, Y., Yano, H., & Tsujii, Y. (2017) · ACS Applied Materials & Interfaces · doi:10.1021/acsami.7b13963 · Cited by 69 · see citing works
Crosslinking of poly(ε-caprolactone) by radiation technique and its biodegradability
Yoshii, F., Darwis, D., Mitomo, H., & Makuuchi, K. (2000) · Radiation Physics and Chemistry · doi:10.1016/s0969-806x(99)00449-1 · Cited by 67 · see citing works
Development of bacterial cellulose and polycaprolactone (PCL) based composite for medical material
Kotcharat, P., Chuysinuan, P., Thanyacharoen, T., Techasakul, S., & Ummartyotin, S. (2021) · Sustainable Chemistry and Pharmacy · doi:10.1016/j.scp.2021.100404 · Cited by 63 · see citing works
Grafting of glycidyl methacrylate onto polycaprolactone: preparation and characterization
Kim, C.-H., Cho, K. Y., & Park, J. (2001) · Polymer · doi:10.1016/s0032-3861(01)00013-1 · Cited by 60 · see citing works
Effect of peroxide crosslinking on thermal and mechanical properties of poly(ε‐caprolactone)
Han, C., Ran, X., Su, X., Zhang, K., Liu, N., & Dong, L. (2007) · Polymer International · doi:10.1002/pi.2156 · Cited by 56 · see citing works
Compatibility between Cellulose and Hydrophobic Polymer Provided by Microfibrillated Lignocellulose
Gindl‐Altmutter, W., Obersriebnig, M., Veigel, S., & Liebner, F. W. (2014) · ChemSusChem · doi:10.1002/cssc.201402742 · Cited by 53 · see citing works
Przybysz-Romatowska, M., Hejna, A., Haponiuk, J. T., & Formela, K. (2019) · Polymers · doi:10.3390/polym11071101 · Cited by 51 · see citing works
Zheng, T., Clemons, C. M., & Pilla, S. (2019) · ACS Sustainable Chemistry & Engineering · doi:10.1021/acssuschemeng.9b04867 · Cited by 48 · see citing works
Re, G. L., Spinella, S., Boujemaoui, A., Vilaseca, F., Larsson, P. T., Adås, F., & Berglund, L. A. (2018) · ACS Sustainable Chemistry & Engineering · doi:10.1021/acssuschemeng.8b00551 · Cited by 47 · see citing works
Re, G. L., Engström, J., Wu, Q., Malmström, E., Gedde, U. W., Olsson, R. T., & Berglund, L. A. (2018) · ACS Applied Nano Materials · doi:10.1021/acsanm.8b00376 · Cited by 42 · see citing works
Melt Processing of Cellulose Nanocrystal-Filled Composites: Toward Reinforcement and Foam Nucleation
Zheng, T., & Pilla, S. (2020) · Industrial & Engineering Chemistry Research · doi:10.1021/acs.iecr.0c00170 · Cited by 42 · see citing works
Mishra, J. K., Chang, Y., & Kim, D. (2006) · Materials Letters · doi:10.1016/j.matlet.2006.11.119 · Cited by 41 · see citing works
Kolahchi, A. R., & Kontopoulou, M. (2015) · Polymer Degradation and Stability · doi:10.1016/j.polymdegradstab.2015.09.008 · Cited by 40 · see citing works
Kaldéus, T., Träger, A., Berglund, L. A., Malmström, E., & Re, G. L. (2019) · ACS Nano · doi:10.1021/acsnano.8b08257 · Cited by 38 · see citing works
Mishra, J. K., Chang, Y., & Kim, W. (2010) · Polymer Bulletin · doi:10.1007/s00289-010-0376-9 · Cited by 37 · see citing works
Germiniani, L. G. L., da Silva, L. C. E., Plivelic, T. S., & Gonçalves, M. D. C. (2018) · Journal of Materials Science · doi:10.1007/s10853-018-2860-9 · Cited by 31 · see citing works
Takamura, M., Nakamura, T., Kawaguchi, S., Takahashi, T., & Koyama, K. (2010) · Polymer Journal · doi:10.1038/pj.2010.42 · Cited by 30 · see citing works
Mouzakis, D. E., & Karger-Kocsis, J. (1998) · Journal of Applied Polymer Science · doi:10.1002/(sici)1097-4628(19980425)68:4 · Cited by 27 · see citing works
Shen, Y., Zhu, W., Papadaki, M. I., Mannan, M. S., Mashuga, C. V., & Cheng, Z. (2019) · Journal of Loss Prevention in the Process Industries · doi:10.1016/j.jlp.2019.04.001 · Cited by 27 · see citing works
A Review of Wet Compounding of Cellulose Nanocomposites
Clemons, C. C., & Sabo, R. C. (2021) · Polymers · doi:10.3390/polym13060911 · Cited by 27 · see citing works
Avella, A., Mincheva, R., Raquez, J., & Re, G. L. (2021) · Polymers · doi:10.3390/polym13040491 · Cited by 24 · see citing works
Self-citationBhagabati, P., Das, D., & Katiyar, V. (2020) · Materials Advances · doi:10.1039/d0ma00517g · Cited by 23 · see citing works
Li, F., Yu, X., Huang, Z., & Liu, D. (2021) · Polymers for Advanced Technologies · doi:10.1002/pat.5264 · Cited by 21 · see citing works
Thermal behaviors of heat shrinkable poly(vinyl chloride) film
Hong, C. K., Maeng, H., Song, K., & Kaang, S. (2009) · Journal of Applied Polymer Science · doi:10.1002/app.29550 · Cited by 20 · see citing works
Functionalization of aliphatic polyesters by nitroxide radical coupling
Cicogna, F., Coiai, S., Rizzarelli, P., Carroccio, S. C., Gambarotti, C., Domenichelli, I., Yang, C., Dintcheva, N. T., Filippone, G., Pinzino, C., et al. (2014) · Polymer Chemistry · doi:10.1039/c4py00641k · Cited by 20 · see citing works
Crosslinking of polycaprolactone in the pre‐gelation region
Gandhi, K. S., Kriz, D., Salovey, R., Narkis, M., & Wallerstein, R. (1988) · Polymer Engineering and Science · doi:10.1002/pen.760282209 · Cited by 17 · see citing works
Gedde, U. W. (1999) · Springer eBooks · doi:10.1007/978-94-011-0543-9_3 · Cited by 14 · see citing works
Wet Feeding Approach for Cellulosic Materials/PCL Biocomposites
Re, G. L., & Sessini, V. (2018) · ACS symposium series · doi:10.1021/bk-2018-1304.ch011 · Cited by 13 · see citing works
Biodegradable polyesters reinforced with eucalyptus fiber: Effect of reactive agents
Nanthananon, P., Seadan, M., Pivsa‐Art, S., Hiroyuki, H., & Suttiruengwong, S. (2017) · AIP conference proceedings · doi:10.1063/1.5016739 · Cited by 12 · see citing works
Venkatesh, A., Forsgren, L., Avella, A., Banke, K., Wahlberg, J., Vilaseca, F., Re, G. L., & Boldizar, A. (2021) · Journal of Applied Polymer Science · doi:10.1002/app.51615 · Cited by 12 · see citing works
Self-citationEffect of Molecular Modification on PCL Foam Formation and Morphology of PCL
Maio, E. D., Iannace, S., Marrazzo, C., Narkis, M., & Nicolais, L. (2005) · Macromolecular Symposia · doi:10.1002/masy.200551019 · Cited by 11 · see citing works
Melt Processing of Ethylene‐Acrylic Acid Copolymer Composites Reinforced with Nanocellulose
Venkatesh, A., Thunberg, J., Sahlin, K., Rigdahl, M., & Boldizar, A. (2020) · Polymer Engineering and Science · doi:10.1002/pen.25351 · Cited by 11 · see citing works
Flagged first, then by citations
Research works printed but not linked: 1
- Darwis D, Mitomo H, Enjoji T, Yoshii F, Makuuchi K. Heat resistance of radiation crosslinked poly(ε-caprolactone). J Appl Polym Sci 1998;68:581-8. Doi: 10.1002/ (SICI)1097-4628(19980425)68:4<581::AID-APP9>3.0.CO;2-I.
Cited by
Sorted by citations
Selvaraj, S., Chauhan, A., Dutta, V., Verma, R., Rao, S. K., Radhakrishnan, A., & Ghotekar, S. K. (2024) · International Journal of Biological Macromolecules · doi:10.1016/j.ijbiomac.2024.130991 · Cited by 94 · see citing works
Promising cellulose–based functional gels for advanced biomedical applications: A review
Li, X., Jiang, G., Wang, G., Zhou, J., Zhang, Y., & Zhao, D. (2024) · International Journal of Biological Macromolecules · doi:10.1016/j.ijbiomac.2024.129600 · Cited by 44 · see citing works
Idumah, C. I., Odera, R. S., Ezeani, E. O., Low, J. H., Tanjung, F. A., Damiri, F., & Luing, W. S. (2023) · Polymer-Plastics Technology and Materials · doi:10.1080/25740881.2023.2204936 · Cited by 39 · see citing works
Jeon, H., Kim, M.-S., Park, S. B., Kim, S., Lee, M., Park, S.-A., Hwang, S. Y., Koo, J. M., Oh, D. X., & Park, J. (2023) · Cellulose · doi:10.1007/s10570-023-05615-9 · Cited by 27 · see citing works
Vidakis, N., Petousis, M., Michailidis, N., David, C., Mountakis, N., Papadakis, V., Sfakiotakis, E., Sagris, D., & Argyros, A. (2024) · Cellulose · doi:10.1007/s10570-024-05851-7 · Cited by 23 · see citing works
Gammino, M., Gioia, C., Maio, A., Scaffaro, R., & Re, G. L. (2024) · ACS Applied Polymer Materials · doi:10.1021/acsapm.4c00514 · Cited by 22 · see citing works
Tailoring cellulose: from extraction and chemical modification to advanced industrial applications
Jahani, A., & Jazayeri, M. H. (2025) · International Journal of Biological Macromolecules · doi:10.1016/j.ijbiomac.2025.142950 · Cited by 17 · see citing works
Lecoublet, M., Ragoubi, M., Leblanc, N., & Koubaa, A. (2023) · Polymer · doi:10.1016/j.polymer.2023.126358 · Cited by 10 · see citing works
Pesaranhajiabbas, E., Mohanty, A. K., Al-Abdul-Wahid, S., & Misra, M. (2024) · SPE Polymers · doi:10.1002/pls2.10121 · Cited by 10 · see citing works
Ngwenya, M., Gumede, T. P., Pérez Camargo, R. A., & Motloung, B. (2025) · Materials · doi:10.3390/ma18225172 · Cited by 9 · see citing works
“For example, Avella et al. [66] demonstrated that treated CNCs improved interfacial adhesion and dispersion within PCL, resulting in enhanced mechanical performance compared to unmodified fillers.”
Scaffaro, R., Mantia, F. P. L., Re, G. L., Titone, V., & Citarrella, M. C. (2025) · Polymers · doi:10.3390/polym18010022 · Cited by 7 · see citing works
Avella, A., Salse, M., Sessini, V., Mincheva, R., & Re, G. L. (2024) · ACS Sustainable Chemistry & Engineering · doi:10.1021/acssuschemeng.4c00012 · Cited by 8 · see citing works
Self-citationDutta, S., Chakraborty, S., Sengupta, S., Acharya, S., Basu, D., & Bandyopadhyay, A. (2024) · Journal of Polymer Research · doi:10.1007/s10965-024-03889-6 · Cited by 6 · see citing works
Soni, M., Mittal, S., Chaudhari, C. V., Maheswari, P. R., Mondal, R. K., Dubey, K. A., & Bhardwaj, Y. K. (2024) · Polymer · doi:10.1016/j.polymer.2024.126881 · Cited by 4 · see citing works
Scarpelli, F., Tatli, B., Koptelova, A., Hirsch, M., Rose, R. D., Brück, W. M., Crispini, A., & Abitbol, T. (2026) · Biomacromolecules · doi:10.1021/acs.biomac.6c00929
- Authors
- Avella, A., Idström, A., Mincheva, R., Nakayama, K., Evenäs, L., Raquez, J.-M., & Lo Re, G.
- Affiliations
- Chalmers University of Technology (SE)
- University of Mons (BE)
- Wallenberg Wood Science Center (SE)
- ORCID
- Venue
- Composites Part A Applied Science and Manufacturing
- Publisher
- Elsevier BV
- Published
- 2022-12
- Volume
- 163
- Pages
- 107166
- ISSN
- 1359-835X (ISSN-L)
- OpenAlex
- W4292641161
- Cited by
- 15
- References
- 49
- Citations by year
- 2026: 1 · 2025: 3 · 2024: 8 · 2023: 3
- FWCI
- 0.88
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Licence
- Locations
- Composites Part A Applied Science and Manufacturing (publishedVersion, cc-by)
- ORBi UMONS (submittedVersion, other-oa)
- PolyPublie (École Polytechnique de Montréal) (submittedVersion)
- Chalmers Research (Chalmers University of Technology) (submittedVersion)
- Funders
- Umeå Universitet
- Topics
- Physical Sciences › Materials Science › Biomaterials › Advanced Cellulose Research Studies
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Materials Science › Polymers and Plastics › Natural Fiber Reinforced Composites
- Keywords
- cellulose nanocrystals, polycaprolactone, bionanocomposites, gel content, shape memory materials, biodegradable plastics, complex viscosity
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