journal article·2019-02Open access

Composites with surface-grafted cellulose nanocrystals (CNC)

Lilian Forsgren, Karin Sahlin-Sjövold, Abhijit Venkatesh, Johannes Thunberg, Roland Kádár, Antal Boldizar, Gunnar Westman, Mikael Rigdahl

Journal of Materials Science· Volume 54· Issue 4

Abstract

Hydroxyazetidinium salts were used to surface-modify cellulose nanocrystals (CNC) by grafting the salts onto the sulphate ester groups on the CNC surfaces. The grafting was confirmed by ζ -potential measurements and by the thermal degradation behaviour of the modified CNC. The thermal stability (onset of degradation) of the CNC was improved by the surface modification (almost 100 °C). Composites containing surface-modified or unmodified CNC (0.1, 1.0 and 10 wt%) with an ethylene-based copolymer as matrix were produced by compression moulding. The thermal stability of the composites was not, however, markedly improved by the surface grafting onto the CNC. It is suggested that this is due to a degrafting mechanism, associated with the alkaline character of the system, taking place at high temperatures. Model experiments indicated, however, that this did not occur at the conditions under which the composites were produced. Furthermore, in the case of a reference based on pH-neutralised polymeric system and modified CNC, an upward shift in the onset of thermal degradation of the composite was observed. The addition of the CNC to the polymer matrix had a strong influence of the mechanical performance. For example, the tensile modulus increased approximately three times for some systems when adding 10 wt% CNC. The surface grafting of the hydroxyazetidinium salts appeared mainly to affect, in a positive sense, the yield behaviour and ductility of the composites. The results of the mechanical testing are discussed in terms of interactions between the grafted units and the matrix material and between the grafted groups.
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Research context

OpenAlex topics: Advanced Cellulose Research Studies · Nanocomposite Films for Food Packaging · Natural Fiber Reinforced Composites

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (39)

Show source-provided references
1. Berggren K, Klason C, Kubát J (1975) Spritzgiessen holzmehlhaltiger Thermoplaste. Kunststoffe 12(2):69–74
2. Kokta BV, Chen R, Daneault C, Valade JL (1983) Use of wood fibers in thermoplastic composites. Polym Compos 4:229–232. https://doi.org/10.1002/pc.75004040710.1002/pc.750040407 ↗
3. Klason C, Kubát J, Strömvall H-E (1984) The efficiency of cellulosic fillers in common thermoplastics. Part 1. Filling without processing aids or coupling agents. Int J Polym Mater 10:159–187. https://doi.org/10.1080/0091403840808026810.1080/00914038408080268 ↗
4. Domininghaus H (1999) Plastics for engineers. Hanser, Munich
5. Miao C, Hamad WY (2013) Cellulose reinforced polymer composites and nano-composites: a critical review. Cellulose 20:2221–2262. https://doi.org/10.1007/s10570-013-0007-310.1007/s10570-013-0007-3 ↗
6. Pickering KL, Aruan Efendy MG, Le TM (2016) A review of recent developments in natural fibre composites and their mechanical performance. Compos A 83:98112. https://doi.org/10.1016/j.compositesa.2015.08.03810.1016/j.compositesa.2015.08.038 ↗
7. Dalväg H, Klason C, Strömvall H-E (1985) The efficiency of cellulosic fillers in common thermoplastics. Part 1. Filling with processing aids and coupling agents. Int J Polym Mater 11:9–38. https://doi.org/10.1080/0091403850807865110.1080/00914038508078651 ↗
8. Trejo-O’Reilly J-A, Cavaille J-Y, Gandini A (1997) The surface chemical modification of cellulosic fibres in view of their use in composite materials. Cellulose 4:305–320. https://doi.org/10.1023/A:101845231012210.1023/A:1018452310122 ↗
9. George J, Sreekala MS, Thomas S (2001) A review on interface modification and characterization of natural fiber reinforced plastic composites. Polym Eng Sci 41:1471–1485. https://doi.org/10.1002/pen.1084610.1002/pen.10846 ↗
10. Baiardo M, Frisoni G, Scandola M, Licciardello A (2002) Surface chemical modification of natural cellulose fibers. J Appl Polym Sci 83:38–45. https://doi.org/10.1002/app.222910.1002/app.2229 ↗
11. Beck-Candanedo S, Roman M, Gray DG (2005) Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions. Biomacromol 6:1048–1054. https://doi.org/10.1021/bm049300p10.1021/bm049300p ↗
12. Boldizar A, Klason C, Kubát J, Näslund P, Sáha P (1987) Prehydrolyzed cellulose as reinforcing filler for thermoplastics. Int J Polym Mater 11:229–262. https://doi.org/10.1080/0091403870807866510.1080/00914038708078665 ↗
13. Favier V, Chanzy H, Cavaillé JY (1995) Polymer nanocomposites reinforced by cellulose whiskers. Macromolecules 28:6365–6367. https://doi.org/10.1021/ma00122a05310.1021/ma00122a053 ↗
14. Samir MASA, Alloin F, Sanches J-Y, Dufresne A (2004) Cellulose nanocrystals reinforced poly(oxyethylene). Polymer 45:4149–4157. https://doi.org/10.1016/j.polymer.2004.0309410.1016/j.polymer.2004.03094 ↗
15. Xu X, Liu F, Jiang L, Zhu JY, Haagenson D, Wiesenborn DP (2013) Cellulose nanocrystals vs. cellulose nanofibrils: a comparative study on their microstructures and effects as polymer reinforcing agents. ACS Appl Mater Interfaces 5:2999–3009. https://doi.org/10.1021/am302624t10.1021/am302624t ↗
16. Ansari F, Galland S, Johansson M, Plummer CJG, Berglund LA (2014) Cellulose nanofiber network for moisture stable, strong and ductile biocomposites and increased epoxy curing rate. Compos A 63:35–44. https://doi.org/10.1016/compositesa.2014.03.01710.1016/compositesa.2014.03.017 ↗
17. Lee K-Y, Aitomäki Y, Berglund LA, Oksman K, Bismark A (2014) On the use of nanocellulose as reinforcement in polymer matrix composites. Compos Sci Technol 105:15–27. https://doi.org/10.1016/j.compscitech.2014.08.03210.1016/j.compscitech.2014.08.032 ↗
18. Ansari F, Skrifvars M, Berglund L (2015) Nanostructured biocomposites based on unsaturated polyester resin and a cellulose nanofiber network. Compos Sci Technol 117:298–306. https://doi.org/10.1016/j.compscitech.2015.07.00410.1016/j.compscitech.2015.07.004 ↗
19. Morelli CL, Belgacem MN, Branciforti MC, Salon MCB, Bras J, Bretas RES (2016) Nanocomposites of PBAT and cellulose nanocrystals modified by in situ polymerization and melt extrusion. Polym Eng Sci 56:1339–1348. https://doi.org/10.1002/pen.2436710.1002/pen.24367 ↗
20. Moberg T, Tang H, Zhou Q, Rigdahl M (2016) Preparation and viscoelastic properties of composite fibres containing cellulose nanofibrils: formation of a coherent fibrillar network. J Nanomater. https://doi.org/10.1155/2016/956923610.1155/2016/9569236 ↗
21. Roman M, Winter WT (2004) Effect of sulfate groups from sulfuric acid hydrolysis on the thermal degradation behavior of bacterial cellulose. Biomacromol 5:1671–1677. https://doi.org/10.1021/bm034519+10.1021/bm034519+ ↗
22. Wang N, Ding E, Cheng R (2007) Thermal degradation behaviors of spherical cellulose nanocrystals with sulfate groups. Polymer 48:3486–3493. https://doi.org/10.1016/j.polymer.2007.03.06210.1016/j.polymer.2007.03.062 ↗
23. Sahlin K, Forsgren L, Moberg T, Bernin D, Rigdahl M, Westman G (2018) Surface treatment of cellulose nanocrystals (CNC): effects on dispersion rheology. Cellulose 25:331–345. https://doi.org/10.1007/s10570-017-1582-510.1007/s10570-017-1582-5 ↗
24. Börjesson M, Sahlin K, Bernin D, Westman G (2018) Increased thermal stability of nanocellulose composites by functionalization of the sulfate groups on cellulose nanocrystals with azetidinium ions. J Appl Polym Sci. https://doi.org/10.1002/app.4596310.1002/app.45963 ↗
25. Ariño R, Boldizar A (2012) Processing and mechanical properties of thermoplastic composites based on cellulose fibers and ethylene-acrylic acid copolymer. Polym Eng Sci 52:1951–1957. https://doi.org/10.1002/pen.2313410.1002/pen.23134 ↗
26. Hasani M, Cranston ED, Westman G, Gray DG (2008) Cationic surface functionalization of cellulose nanocrystals. Soft Matter 4:2238–2244. https://doi.org/10.1039/b806789a10.1039/b806789a ↗
27. Moberg T, Sahlin K, Yao K, Geng S, Westman G, Zhou Q, Oksman K, Rigdahl M (2017) Rheological properties of nanocellulose suspensions: effects of fibril/particle dimensions and surface characteristics. Cellulose 24:2499–2510. https://doi.org/10.1007/s10570-017-1283-010.1007/s10570-017-1283-0 ↗
28. Chattopadhyay S, Keul H, Moeller M (2012) Functional polymers bearing reactive azetidinium groups: synthesis and characterization. Macromol Chem Phys 213:500–512. https://doi.org/10.1002/macp.20110048010.1002/macp.201100480 ↗
29. Nielsen LE (1974) Mechanical properties of polymers and composites. vol 2, Marcel Dekker Inc, New York, pp 405–415; 422–429
30. Kubát J, Rigdahl M, Welander M (1990) Characterization of interfacial interactions in high density polyetlylene filled with glass spheres using dynamic-mechanical analysis. J Appl Polym Sci 39:1527–1539. https://doi.org/10.1002/app.1990.07039071110.1002/app.1990.070390711 ↗
31. Brandrup J, Immergut E, Grulke E (1999) Polymer handbook, 4th edn. Wiley, Hoboken
32. Venkatesh A, Thunberg J, Moberg T, Klingberg M, Hammar L, Peterson A, Müller C, Boldizar A (2018) Cellulose nanofibril-reinforced composites using aqueous dispersed ethylene-acrylic acid copolymer. Cellulose. https://doi.org/10.1007/s10570-018-1875-310.1007/s10570-018-1875-3 ↗
33. Allen NS, Lo D, Salim MS, Jennings P (1990) Influence of amine structure on the post-cured photoyellowing of novel amine diacrylate terminated ultraviolet and electron beam cured coatings. Polym Degrad Stab 28:105–114. https://doi.org/10.1016/0141-3910(90)90055-C10.1016/0141-3910(90)90055-C ↗
34. Xiao P, Shi S, Nie J (2008) Synthesis and characterization of copolymerizable one-component type II photoinitiators. Polym Adv Technol 19:1305–1310. https://doi.org/10.1002/pat.113210.1002/pat.1132 ↗
35. Matthews FL, Rawlings RD (1994) Composites materials: engineering and science. Chapman & Hall, London
36. McCrum NG, Buckley CP, Bucknall CB (1997) Principles of polymer engineering, 2nd edn. Oxford Science Publications, Oxford
37. Tanpichai S, Quero F, Nogi M, Yano H, Young RJ, Lindström T, Sampson WW, Eichorn SJ (2012) Effective Young’s modulus of bacterial and microfibrillated cellulose fibrils in fibrous networks. Biomacromol 13:1340–1349. https://doi.org/10.1021/bm300042t10.1021/bm300042t ↗
38. Salmén L, Rigdahl M (1984) Dynamic mechanical properties of paper: effect of density and drying restraints. J Mater Sci 19:2955–2961. https://doi.org/10.1007/bf0102697310.1007/bf01026973 ↗
39. Wakabayashi K, Register RA (2006) Morphological origin of the multistep relaxation behavior in semicrystalline ethylene/methacrylic ionomers. Macromolecules 39:1079–1086. https://doi.org/10.1021/ma052081v10.1021/ma052081v ↗