Abstract
alkali-washed nanofibrillated cellulose (NFC) samples, obtained from hardwood kraft pulp, with different amounts of retained xylan were prepared to study the influence of xylan on the water-retention properties of NFC suspensions. In this study, NFC was produced using an oxoammonium-catalyzed oxidation reaction that converts the cellulosic substrate to a more highly oxidized material via the action of the nitroxide radical species 2,2,6,6-tetramethylpiperidine-1-oxyl. Reduction of the xylan content in NFC was achieved by cold alkali extraction of kraft pulp. The pulps were then oxidized to a set charge under constant chemical conditions, and the reaction time was determined. The xylan content of the feed pulp was found to have a large negative influence on the oxidation rate of the pulp, as the oxidation time shortened when xylan was removed, from 220 min (for 25.2 % xylan content) to 28 min (for 7.3 % xylan content). Following fibrillation by homogenization, the swelling of the NFC was determined by a two-point solute exclusion method. The distribution of hemicellulose over the fibril surface was observed by atomic force microscopy. Xylan was found to be distributed unevenly over the surface, and its presence increased the water immobilized within flocs of NFC, i.e., so-called network swelling. The swelling of the NFC had a large impact on its rheology and dewatering. Comparison of the morphological and swelling properties of the suspensions with their rheological and dynamic dewatering behavior showed that reducing the xylan content in NFC results in a weaker gel structure of the nanocellulose suspension. The results indicate that most of the water is held by the swollen structure by means of xylan particles trapped within the hemicellulose layer covering the fibril surface. Samples with high xylan content had high shear modulus and viscosity and were difficult to dewater.
Similar content being viewed by others
References
Agoda-Tandjawa G, Durand S, Berot S, Blassel C, Gaillard C, Garnier C, Doublier J (2010) Rheological characterization of microfibrillated cellulose suspensions after freezing. Carbohydr Polym 80:677–686
Anelli PL, Biffi C, Montanari F, Quici S (1987) Fast and selective oxidation of primary alcohols to aldehydes or to carboxylic acids and of secondary alcohols to ketones mediated by oxoammonium salts under two-phase conditions. J Org Chem 52(12):2559–2562
Araki J, Wada M, Kuga S (2000) Steric stabilization of a cellulose microcrystal suspension by poly (ethylene glycol) grafting. Langmuir 17(1):21–27
Ayol A, Dentel S, Filibeli A (2010) Rheological characterization of sludges during belt filtration dewatering using an immobilization cell. J Environ Eng 136(9):992–999
Barnes HA (2007) The “yield stress myth?” paper - 21 years. Appl Rheol 17(4):43110–44250
Barnes HA, Ngyen QD (2001) Rotating vane rheometry-a review. J Non Newtonian Fluid Mech 98(1):1–14
Bennington CPJ, Kerekes RJ, Grace JR (1990) The yield stress of fibre suspensions. Can J Chem Eng 68:748–757
Besseling R, Isa L, Ballesta P, Petekidis G, Cates M, Poon W (2010) Shear banding and flow-concentration coupling in colloidal glasses. Phys Rev Lett 105(26):268–301
Bragd PL, van Bekkum H, Besemer AC (2004) TEMPO-mediated oxidation of polysaccharides: survey of methods and applications. Top Catal 27(1–4):49–66
Bulota M, Vesterinen A, Hughes M, Seppälä J (2013) Mechanical behavior, structure, and reinforcement processes of TEMPO-oxidized cellulose reinforced poly(lactic) acid. Polym Compos 34(2):173–179
Buscall R, Mills P, Stewart R, Sutton D, White L, Yates G (1987) The rheology of strongly-flocculated suspensions. J Non Newtonian Fluid Mech 24(2):183–202
Chen W, Li Q, Wang Y, Yi X, Zeng J, Yu H, Liu Y, Li J (2014) Comparative study of aerogels obtained from differently prepared nanocellulose fibers. ChemSusChem 7(1):154–161
Cheng DC (1986) Yield stress: a time-dependent property and how to measure it. Rheol Acta 25(5):542–554
Damani R, Powell RL, Hagen N (1993) Viscoelastic characterization of medium consistency pulp suspensions. Can J Chem Eng 71(5):676–684
de Nooy AEJ, Besemer AC, van Bekkum H (1995) Selective oxidation of primary alcohols mediated by nitroxyl radical in aqueous solution. Tetrahedron 51(29):8023–8032
Deka A, Dey N (2013) Rheological studies of two component high build epoxy and polyurethane based high performance coatings. J Coat Technol Res 10(3):305–315
Derakhshandeh B, Kerekes RJ, Hatzikiriakos SG, Bennington CPJ (2011) Rheology of pulp fibre suspensions: a critical review. Chem Eng Sci 66(15):3460–3470
Dimic-Misic K, Puisto A, Gane P, Nieminen K, Alava M, Paltakari J, Maloney T (2013a) The role of MFC/NFC swelling in the rheological behavior and dewatering of high consistency furnishes. Cellulose 20(6):2847–2861
Dimic-Misic K, Puisto A, Paltakari J, Alava M, Maloney T (2013b) The influence of shear on the dewatering of high consistency nanofibrillated cellulose furnishes. Cellulose 20(4):1853–1864
Dimic-Misic K, Nieminen K, Gane P, Maloney T, Sixta H, Paltakari J (2014) Deriving a process viscosity for complex particulate nanofibrillar cellulose gel-containing suspensions. Appl Rheol 24:35616–35625
Divoux T, Barentin C, Manneville S (2011) From stress-induced fluidization processes to Herschel–Bulkley behaviour in simple yield stress fluids. Soft Matter 7(18):8409–8418
Divoux T, Grenard V, Manneville S (2013) Rheological hysteresis in soft glassy materials. Phys Rev Lett 110(1):8409–8418
Duchesne I, Hult E, Molin U, Daniel G, Iversen T, Lennholm H (2001) The influence of hemicellulose on fibril aggregation of kraft pulp fibres as revealed by FE-SEM and CP/MAS 13C-NMR. Cellulose 8(2):103–111
Dullaert K, Mewis J (2006) A structural kinetics model for thixotropy. J Non Newtonian Fluid Mech 139(1):21–30
Fall AB, Lindström SB, Sundman O, Ödberg L, Wagberg L (2011) Colloidal stability of aqueous nanofibrillated cellulose dispersions. Langmuir 27(18):11332–11338
Fukuzumi H, Saito T, Iwata T, Kumamoto Y, Isogai A (2008) Transparent and high gas barrier films of cellulose nanofibers prepared by TEMPO-mediated oxidation. Biomacromolecules 10(1):162–165
Fukuzumi H, Tanaka R, Saito T, Isogai A (2014) Dispersion stability and aggregation behavior of TEMPO-oxidized cellulose nanofibrils in water as a function of salt addition. Cellulose 21(3):1553–1559
Grönqvist S, Hakala TK, Kamppuri T, Vehviläinen M, Hänninen T, Liitiä T, Maloney T, Suurnäkki A (2014) Fibre porosity development of dissolving pulp during mechanical and enzymatic processing. Cellulose 21(5):3667–3676
Hatakeyama T, Inui Y, Iijima M, Hatakeyama H (2013) Bound water restrained by nanocellulose fibres. J Therm Anal Calorim 113(3):1019–1025
Hirokawa Y, Tanaka T (1984) Volume phase transition in a nonionic gel. J Chem Phys 81(12):6379–6380
Horvath AE, Lindström T (2007) The influence of colloidal interactions on fiber network strength. J Colloid Interface Sci 309(2):511–517
Iguchi M, Yamanaka S, Budhiono A (2000) Bacterial cellulose—a masterpiece of nature’s arts. J Mater Sci 35(2):261–270
Iotti M, Gregersen O, Weiby MoeS, Lenes M (2011) Rheological studies of microfibrillar cellulose water dispersions. J Polym Environ 19(1):137–145
Ishii D, Saito T, Isogai A (2011) Viscoelastic evaluation of average length of cellulose nanofibers prepared by TEMPO-mediated oxidation. Biomacromolecules 12(3):548–550
Isogai A, Kato Y (1998) Preparation of polyuronic acid from cellulose by TEMPO-mediated oxidation. Cellulose 5(3):153–164
Isogai T, Saito T, Isogai A (2010) TEMPO electromediated oxidation of some polysaccharides including regenerated cellulose fiber. Biomacromolecules 11(6):1593–1599
Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3(1):71–85
Iwamoto S, Isogai A, Iwata T (2011) Structure and mechanical properties of wet-spun fibers made from natural cellulose nanofibers. Biomacromolecules 12(3):831–836
Jäder J, Järnstrom L (2003) The influence of thickener addition on filter cake formation during dewatering of mineral suspensions. Appl Rheol 13(3):125–131
Jiang F, Hsieh Y (2014) Super water absorbing and shape memory nanocellulose aerogels from TEMPO-oxidized cellulose nanofibrils via cyclic freezing-thawing. J Mater Chem A 2(2):350–359
Karppinen A, Saarinen T, Salmela J, Laukkanen A, Nuopponen M, Seppälä J (2012) Flocculation of microfibrillated cellulose in shear flow. Cellulose 19(6):1807–1819
Kavanagh GM, Ross-Murphy SB (1998) Rheological characterisation of polymer gels. Prog Polym Sci 23(2):533–562
Kitaoka T, Isogai A, Onabe F (1999) Chemical modification of pulp fibers by TEMPO-mediated oxidation. Nord Pulp Pap Res J 14(4):279–284
Klemm D, Kramer F, Moritz S, Lindström T, Ankerfors M, Gray D, Dorris A (2011) Nanocelluloses: a new family of nature-based materials. Angew Chem Int Ed 50(24):5438–5466
Koga H, Saito T, Kitaoka T, Nogi M, Suganuma K, Isogai A (2013) Transparent, conductive, and printable composites consisting of TEMPO-oxidized nanocellulose and carbon nanotube. Biomacromolecules 14(4):1160–1165
Lasseuguette E, Roux D, Nishiyama Y (2008) Rheological properties of microfibrillar suspension of TEMPO-oxidized pulp. Cellulose 15(3):425–433
Laudone G, Matthews G, Gane P (2006) Effect of latex volumetric concentration on void structure, particle packing, and effective particle size distribution in a pigmented paper coating layer. Ind Eng Chem Res 45(6):1918–1923
Läuger J, Wollny K, Huck S (2002) Direct strain oscillation: a new oscillatory method enabling measurements at very small shear stresses and strains. Rheol Acta 41(4):356–361
Lee K, Bismarck A (2012) Susceptibility of never-dried and freeze-dried bacterial cellulose towards esterification with organic acid. Cellulose 19(3):891–900
Lindström T, Carlsson G (1982) The effect of chemical environment on fiber swelling. Svensk Papperstindning-Nordisk Cellulosa 85(3):14–20
Littunen K, Hippi U, Saarinen T, Seppälä J (2013) Network formation of nanofibrillated cellulose in solution blended poly (methyl methacrylate) composites. Carbohydr Polym 91(1):183–190
Lowys M, Desbrieres J, Rinaudo M (2001) Rheological characterization of cellulosic microfibril suspensions. Role of polymeric additives. Food Hydrocoll 15(1):25–32
Maloney TC (2015) Network swelling of TEMPO-oxidized nanocellulose. Holzforschung 69(2):207–213
Manninen M, Nieminen K, Maloney TC (2013) The swelling and pore structure of microfibrillated cellulose. In: 15 the Fundamental research syposium, conference proceedings. Cambridge, UK, pp 725–738
Meng Q, Li H, Fu S, Lucia LA (2014) The non-trivial role of native xylans on the preparation of TEMPO-oxidized cellulose nanofibrils. React Funct Polym 85:142–150
Mewis J, Wagner NJ (2009) Thixotropy. Adv Colloid Interface Sci 147:214–227
Moan M, Aubry T, Bossard F (2003) Nonlinear behavior of very concentrated suspensions of plate-like kaolin particles in shear flow. J Rheol 47(6):1493–1504
Mohtaschemi M, Dimic-Misic K, Puisto A, Korhonen M, Maloney T, Paltakari J, Alava M (2014) Rheological characterization of fibrillated cellulose suspensions via bucket vane viscometer. Cellulose 21(3):1305–1312
Møller PC, Mewis J, Bonn D (2006) Yield stress and thixotropy: on the difficulty of measuring yield stresses in practice. Soft Matter 2(4):274–283
Naderi A, Lindström T, Pettersson T (2014) The state of carboxymethylated nanofibrils after homogenization-aided dilution from concentrated suspensions: a rheological perspective. Cellulose 21(4):2357–2368
Nechyporchuk O, Belgacem MN, Pignon F (2015) Concentration effect of TEMPO-oxidized nanofibrillated cellulose aqueous suspensions on the flow instabilities and small-angle X-ray scattering structural characterization. Cellulose 22(4):2197–2210
Nguyen Q, Boger D (1992) Measuring the flow properties of yield stress fluids. Annu Rev Fluid Mech 24:47–88
Okita Y, Saito T, Isogai A (2010) Entire surface oxidation of various cellulose microfibrils by TEMPO-mediated oxidation. Biomacromolecules 11(6):1696–1700
Orelma H, Filpponen I, Johansson L, Österberg M, Rojas O, Laine J (2012) Surface functionalized nanofibrillar cellulose (NFC) film as a platform for immunoassays and diagnostics. Biointerphases 7(1):61–73
Ovarlez G, Rodts S, Chateau X, Coussot P (2009) Phenomenology and physical origin of shear localization and shear banding in complex fluids. Rheol Acta 48(8):831–844
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(6):1934–1941
Pönni R, Pääkkönen T, Nuopponen M, Pere J, Vuorinen T (2014) Alkali treatment of birch kraft pulp to enhance its TEMPO catalyzed oxidation with hypochlorite. Cellulose 21(4):2859–2869
Puisto A, Illa X, Mohtaschemi M, Alava M (2012a) Modeling the viscosity and aggregation of suspensions of highly anisotropic nanoparticles. Eur Phys J E 35(1):1–7
Puisto A, Illa X, Mohtaschemi M, Alava M (2012b) Modeling the rheology of nanocellulose suspensions. Nord Pulp Pap Res J 27(2):277–281
Richmond F, Co A, Bousfield D (2012) The coating of nanofibrillated cellulose onto paper using flooded and metered size press methods. New Orleans 12PaperCon. Papers/12PAP18 aspx
Saarikoski E, Saarinen T, Salmela J, Seppälä J (2012) Flocculated flow of microfibrillated cellulose water suspensions: an imaging approach for characterisation of rheological behaviour. Cellulose 19(3):647–659
Saito T (2005) Distribution of carboxylate groups introduced into cotton linters by the TEMPO-mediated oxidation. Carbohydr Polym 61(4):414–419
Saito T, Okita Y, Nge TT, Sugiyama J, Isogai A (2006) TEMPO-mediated oxidation of native cellulose: microscopic analysis of fibrous fractions in the oxidized products. Carbohydr Polym 65(4):435–440
Saito T, Kimura S, Nishiyama Y, Isogai A (2007) Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules 8(8):2485–2491
Sehaqui H, Zhou Q, Berglund LA (2011) High-porosity aerogels of high specific surface area prepared from nanofibrillated cellulose (NFC). Compos Sci Technol 71(13):1593–1599
Semmelhack MF, Chou CS, Cortes DA (1983) Nitroxyl-mediated electrooxidation of alcohols to aldehydes and ketones. J Am Chem Soc 105(13):4492–4494
Semmelhack MF, Schmid CR, Cortes DA, Chou CS (1984) Oxidation of alcohols to aldehydes with oxygen and cupric ion, mediated by nitrosonium ion. J Am Chem Soc 106(11):3374–3376
Shih WY, Shih WH, Aksay IA (1999) Elastic and yield behavior of strongly flocculated colloids. J Am Ceram Soc 82(3):616–624
Siró I (2010) Microfibrillated cellulose and new nanocomposite materials: a review. Cellulose 17(3):459–494
Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Templeton D, Crocker D (2008) Determination of structural carbohydrates and lignin in biomass. NREL/TP-510-42618 NREL Laboratory Analytical Procedure. National Renewable Energy Laboratory, Golden. http://www.nrel.gov/biomass/pdfs/42618.pdf
Tanaka R, Saito T, Isogai A (2012) Cellulose nanofibrils prepared from softwood cellulose by TEMPO/NaClO/NaClO2 systems in water at pH 4.8 or 6.8. Int J Biol Macromol 51(3):228–234
Tenhunen T, Peresin MS, Penttilä PA, Pere J, Serimaa R, Tammelin T (2014) Significance of xylan on the stability and water interactions of cellulosic nanofibrils. React Funct Polym 85:157–166
Van Hecke M (2005) Granular matter: a tale of tails. Nature 435(7045):1041–1042
Wågberg L, Decher G, Norgren M, Lindström T, Ankerfors M, Axnäs K (2008) The build-up of polyelectrolyte multilayers of microfibrillated cellulose and cationic polyelectrolytes. Langmuir 24(3):784–795
Walls HJ, Caines SB, Sanchez AM, Khan SA (2003) Yield stress and wall slip phenomena in colloidal silica gels. J Rheol 47(4):847–868
Walther A, Timonen JVI, Díez I, Laukkanen A, Ikkala O (2011) Multifunctional high-performance biofibers based on wet-extrusion of renewable native cellulose nanofibrils. Adv Mater 23(26):2924–2928
Wollny K (2001) New rheological test method to determine the dewatering kinetics of suspensions. Appl Rheol 11:202
Yang MC, Scriven LE, Macosko CW (1986) Some rheological measurements on magnetic iron oxide suspensions in silicone oil. J Rheol 30(5):1015–1029
Yusuke Okita, Tsuguyuki Saito, Akira Isogai (2009) TEMPO-mediated oxidation of softwood thermomechanical pulp. Holzforschung 63(5):529–535
Acknowledgments
The Academy of Finland is thanked for supporting this research. The authors thank Mr. Antton Lahnalammi for performing TEMPO-mediated oxidation of birch pulp samples and Ms. Anu Anttila for performing fluidization of TEMPO-oxidized pulp solutions. Ms. Ritva Kivelä is acknowledged for technical assistance with AFM imaging. We also thank Ms. Mirja Reinikainen, Ms. Tuyen Nguyen, and Ms. Leena Nolvi for excellent laboratory work.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Pääkkönen, T., Dimic-Misic, K., Orelma, H. et al. Effect of xylan in hardwood pulp on the reaction rate of TEMPO-mediated oxidation and the rheology of the final nanofibrillated cellulose gel. Cellulose 23, 277–293 (2016). https://doi.org/10.1007/s10570-015-0824-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-015-0824-7