Abstract
Water-redispersible, nanofibrillated cellulose (NFC) in powder form was prepared from refined, bleached beech pulp (RBP) by carboxymethylation (c) and mechanical disintegration (m). Two routes were examined by altering the sequence of the chemical and mechanical treatment, leading to four different products: RBP-m and RBP-mc (route 1), and RBP-c and RBP-cm (route 2). The occurrence of the carboxymethylation reaction was confirmed by FT-IR spectrometry and 13C solid state NMR (13C CP-MAS) spectroscopy with the appearance of characteristic signals for the carboxylate group at 1,595 cm−1 and 180 ppm, respectively. The chemical modification reduced the crystallinity of the products, especially for those of route 2, as shown by XRD experiments. Also, TGA showed a decrease in the thermal stability of the carboxymethylated products. However, sedimentation tests revealed that carboxymethylation was critical to obtain water-redispersible powders: the products of route 2 were easier to redisperse in water and their aqueous suspensions were more stable and transparent than those from route 1. SEM images of freeze-dried suspensions from redispersed RBP powders confirmed that carboxymethylation prevented irreversible agglomeration of cellulose fibrils during drying. These results suggest that carboxymethylated and mechanically disintegrated RBP in dry form is a very attractive alternative to conventional NFC aqueous suspensions as starting material for derivatization and compounding with (bio)polymers.
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Abe K, Iwamoto S, Yano H (2007) Obtaining cellulose nanofibers with a uniform width of 15 nm from wood. Biomacromolecules 8:3276–3278
Andresen M, Johansson LS, Tanem BS, Stenius P (2006) Properties and characterization of hydrophobized microfibrillated cellulose. Cellulose 13:665–677
Araki J, Wada M, Kuga S (2001) Steric stabilization of a cellulose microcrystal suspension by poly(ethylene glycol) grafting. Langmuir 17:21–27
Bahia HS (1995) Treatment of cellulose. Patent publication number WO9515342
Boldizar A, Klason C, Kubat J (1987) Prehydrolyzed cellulose as reinforcing filler for thermoplastics. Int J Polym Mater 11:229–262
Bordeanu N, Eyholzer Ch, Zimmermann T (2008) Cellulose nanostructures with tailored functionalities. Pending patent
Cantiani R, Guerin G, Senechal A, Vincent I, Benchimol J (2001) Patent publication numbers US6224663, US6231657, US6306207
Cash MJ, Chan AN, Conner HT, Cowan PJ, Gelman RA, Lusvardi KM, Thompson SA, Tise FP (2003) Derivatized microfibrillar polysaccharide. Patent publication number WO0047628
Chakraborty A, Sain M, Kortschot M (2006) Reinforcing potential of wood pulp-derived microfibres in a PVA matrix. Holzforschung 60:53–58
Couderc S, Ducloux O, Kim BJ, Someya T (2009) A mechanical switch device made of a polyimide-coated microfibrillated cellulose sheet. J Micromech Microeng 19:055006
Cuba-Chiem LT, Huynh L, Ralston J, Beattie DA (2008) In situ particle film ATR FTIR spectroscopy of carboxymethyl cellulose adsorption on talc: binding mechanism, pH effects, and adsorption kinetics. Langmuir 24:8036–8044
Dinand E, Chanzy H, Vignon M, Maureaux A, Vincent I (1996) Microfibrillated cellulose and method for preparing same from primary wall plant pulp, particularly sugar beet pulp. Patent publication number WO9624720
Excoffier G, Vignon M, Benchimol J, Vincent I, Hannuksela T, Chauve V (1999) Parenchyma cellulose substituted with carboxyalkyl groups and preparation method. Patent publication number WO9938892
Eyler RW, Klug ED, Diephuis F (1947) Determination of degree of substitution of sodium carboxymethylcellulose. Anal Chem 19:24–27
Fukuzumi H, Saito T, Iwata T, Kumamoto Y, Isogai A (2009) Transparent and high gas barrier films of cellulose nanofibers prepared by TEMPO-mediated oxidation. Biomacromolecules 10:162–165
Gilardi G, Abis L, Cass AEG (1995) Carbon-13 CP/MAS solid-state NMR and FT-IR spectroscopy of wood cell wall biodegradation. Enzyme Microb Technol 17:268–275
Goussé C, Chanzy H, Cerrada ML, Fleury E (2004) Surface silylation of cellulose microfibrils: preparation and rheological properties. Polymer 45:1569–1575
Heinze T, Koschella A (2005) Carboxymethyl ethers of cellulose and starch—a review. Macromol Symp 223:13–39
Herrick FW (1984) Process for preparing microfibrillated cellulose. Patent publication number US4481077
Herrick FW, Casebier RL, Hamilton JK, Sandberg KR (1983) Microfibrillated cellulose: morphology and accessibility. J Appl Polym Sci: Appl Polym Symp 37:797–813
Hubbe MA, Rojas OJ, Lucia LA, Sain M (2008) Cellulosic nanocomposites: a review. Biores 3:929–980
Hult EL, Larsson PT, Iversen T (2001) Cellulose fibril aggregation—an inherent property of kraft pulps. Polymer 42:3309–3314
Kono H, Yunoki S, Shikano T, Fujiwara M, Erata T, Takai M (2002) CP/MAS 13C NMR study of cellulose and cellulose derivatives. 1. Complete assignment of the CP/MAS 13C NMR spectrum of the native cellulose. J Am Chem Soc 124:7506–7511
Laivins GV, Scallan AM (1993) The mechanism of hornification of wood pulps. In: Proc 10th fundamental research sympoisum. Oxford, pp 1235–1260
Lasseuguette E (2008) Grafting onto microfibrils of native cellulose. Cellulose 15:571–580
Lindström T, Carlsson G (1982) The effect of carboxyl groups and their ionic form during drying on the hornification of cellulose fibers. Svensk Papperstidning 85:R146–R151
Lourdes-Leza M, Cortazar M, Casinos I, Guzmán GM (1989) Thermal degradation of partially carboxymethylated cellulose grafted with 4-vinylpyridine. Angew Makromol Chem 168:195–203
Pääkkö M, Ankerfors M, Kosonen H, Nykänen A, Ahola S, Österberg M, Ruokolainen J, Laine J, Larsson PT, Ikkala O, Lindström T (2007) Enzymatic hydrolysis combined with mechanical shearing and high-pressure homogenization for nanoscale cellulose fibrils and strong gels. Biomacromolecules 8:1934–1941
Proniewicz LM, Paluszkiewicz C, Weselucha-Birczyńska A, Majcherczyk H, Barański A, Konieczna A (2001) FT-IR and FT-Raman study of hydrothermally degradated cellulose. J Mol Struct 596:163–169
Reid JD, Daul GC (1947) The partial carboxymethylation of cotton to obtain swellable fibers, I. Text Res J 17:554–561
Saito T, Nishiyama Y, Putaux JL, Vignon M, Isogai A (2006) Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose. Biomacromolecules 7:1687–1691
Sassi JF, Chanzy H (1995) Ultrastructural aspects of the acetylation of cellulose. Cellulose 2:111–127
Scallan AM, Tigerström AC (1992) Swelling and elasticity of the cell walls of pulp fibres. J Pulp Pap Sci 18:188–193
Segal L, Creely JJ, Martin AE Jr, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-Ray diffractometer. Text Res J 29:786–794
Shafizadeh F, McGinnis GD (1971) Chemical composition and thermal analysis of cottonwood. Carbohydr Res 16:273–277
Stenstad P, Andresen M, Tanem BS, Stenius P (2008) Chemical surface modifications of microfibrillated cellulose. Cellulose 15:35–45
Turbak AF, Snyder FW, Sandberg KR (1983) Microfibrillated cellulose, a new cellulose product: properties, uses, and commercial potential. J Appl Polym Sci: Appl Polym Symp 37:815–823
Wågberg L, Winter L, Ödberg L, Lindström T (1987) On the charge stoichiometry upon adsorption of a cationic polyelectrolyte on cellulosic materials. Colloid Surfaces 27:163–173
Wågberg L, Decher G, Norgren M, Lindström T, Ankerfors M, Axns K (2008) The build-up of polyelectrolyte multilayers of microfibrillated cellulose and cationic polyelectrolytes. Langmuir 24:784–795
Walecka JA (1956) An investigation of low degree of substitution carboxymethylcelluloses. Tappi 39:458–463
Yano H, Nakahara S (2004) Bio-composites produced from plant microfiber bundles with a nanometer unit web-like network. J Mater Sci 39:1635–1638
Yano H, Sugiyama J, Nakagaito AN, Nogi M, Matsuura T, Hikita M, Handa K (2005) Optically transparent composites reinforced with networks of bacterial nanofibers. Adv Mater 17:153–155
Young RA (1994) Comparison of the properties of chemical cellulose pulps. Cellulose 1:107–130
Zadorecki P, Michell AJ (1989) Future-prospects for wood cellulose as reinforcement in organic polymer composites. Polym Compos 10:69–77
Acknowledgments
The authors wish to express their thanks to Beatrice Fischer, as well as Urs Gfeller and Dr. Peter Lienemann for performing the TGA and XRD measurements, respectively and Dr. Philippe Tingaut for carefully reading the manuscript. The authors gratefully acknowledge the State Secretariat for Education and Research (SER) for financial support of this work.
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Eyholzer, C., Bordeanu, N., Lopez-Suevos, F. et al. Preparation and characterization of water-redispersible nanofibrillated cellulose in powder form. Cellulose 17, 19–30 (2010). https://doi.org/10.1007/s10570-009-9372-3
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DOI: https://doi.org/10.1007/s10570-009-9372-3