Abstract
Cellulose nanocrystals (CNCs) are ideal rheological modifiers for aqueous oil and gas extraction fluids. CNCs are typically produced with sulfuric acid and their aqueous suspensions have uniform and predictable properties under ambient conditions; however, drastic changes occur at elevated temperatures. Herein, the effects of high temperature treatments (ranging from 80 to 180 °C for 1 h to 7 days) on the properties (including uniformity, colloidal stability, and color) of sulfated, phosphated, and carboxylated CNC suspensions were studied. Additionally, cellulose molecular weight, and CNC surface charge content and crystallinity index were quantified before and after heating. CNCs underwent few morphological changes; their molecular weight and crystallinity index were largely unchanged under the conditions tested. Their surface charge content, however, was significantly decreased after heat treatment which resulted in loss of colloidal stability and aggregation of CNCs. The largest change in suspension properties was observed for sulfated CNCs whereas CNCs with a combination of sulfate and phosphate esters, or carboxylate groups, were less affected and maintained colloidal stability at higher temperatures. In fact, desulfation was found to occur rapidly at 80 °C, while many carboxylate groups persisted at temperatures up to 180 °C; calculated rate constants (based on second order kinetics) suggested that desulfation is 20 times faster than decarboxylation but with a similar activation energy. Overall, this study elucidates CNC suspension behavior after heat exposure and demonstrates routes to produce CNCs with improved high temperature performance.
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References
Aadland RC, Jakobsen TD, Heggset EB et al (2019) High-temperature core flood investigation of nanocellulose as a green additive for enhanced oil recovery. Nanomaterials. https://doi.org/10.3390/nano9050665
Abitbol T, Kam D, Levi-Kalisman Y et al (2018) Surface charge influence on the phase separation and viscosity of cellulose nanocrystals. Langmuir 34:3925–3933. https://doi.org/10.1021/acs.langmuir.7b04127
Agustin MB, Nakatsubo F, Yano H (2016) The thermal stability of nanocellulose and its acetates with different degree of polymerization. Cellulose 23:451–464. https://doi.org/10.1007/s10570-015-0813-x
Andrews MP, Morse T (2017) Method for producing functionalized nanocrystalline cellulose and functionalized nanocrystalline cellulose thereby produced
Araki J, Wada M, Kuga S, Okano T (1998) Flow properties of microcrystalline cellulose suspension prepared by acid treatment of native cellulose. Colloids Surf A Physicochem Eng Asp 142:75–82. https://doi.org/10.1016/S0927-7757(98)00404-X
Araki J, Wada M, Kuga S (2001) Steric stabilization of a cellulose microcrystal suspension by poly(ethylene glycol) grafting. Langmuir 17:21–27. https://doi.org/10.1021/la001070m
Bashir Wani O, Shoaib M, Al Sumaiti A et al (2020) Application of Green additives for enhanced oil recovery: cellulosic nanocrystals as fluid diversion agents in carbonate reservoirs. Colloids Surf A Physicochem Eng Asp. https://doi.org/10.1016/j.colsurfa.2020.124422
Battista OA, Coppick S, Howsmon JA et al (1956) Level-off degree of polymerization. Ind Eng Chem 48:333–335. https://doi.org/10.1021/ie50554a046
Beck S, Bouchard J (2014) Auto-catalyzed acidic desulfation of cellulose nanocrystals. Nord Pulp Pap Res J 29:6–14. https://doi.org/10.3183/NPPRJ-2014-29-01-p006-014
Beck S, Méthot M, Bouchard J (2015) General procedure for determining cellulose nanocrystal sulfate half-ester content by conductometric titration. Cellulose 22:101–116. https://doi.org/10.1007/s10570-014-0513-y
Bhattacharjee S (2016) DLS and zeta potential—what they are and what they are not? J Control Release 235:337–351. https://doi.org/10.1016/j.jconrel.2016.06.017
Bouchard J, Méthot M, Fraschini C, Beck S (2016) Effect of oligosaccharide deposition on the surface of cellulose nanocrystals as a function of acid hydrolysis temperature. Cellulose 23:3555–3567. https://doi.org/10.1007/s10570-016-1036-5
Camarero Espinosa S, Kuhnt T, Foster EJ et al (2013) Isolation of thermally stable cellulose nanocrystals by phosphoric acid hydrolysis. Biomacromol 14:1223–1230. https://doi.org/10.1021/bm400219u
Chen L, Zhu J, Baez C et al (2016) Highly thermal-stable and functional cellulose nanocrystals and nanofibrils produced using fully recyclable organic acids. Green Chem 18:3835–3843. https://doi.org/10.1039/C6GC00687F
Cherhal F, Cousin F, Capron I (2015) Influence of charge density and ionic strength on the aggregation process of cellulose nanocrystals in aqueous suspension, as revealed by small-angle neutron scattering. Langmuir 31:5596–5602. https://doi.org/10.1021/acs.langmuir.5b00851
Conner AH (1995) Size exclusion chromatography of cellulose and cellulose derivatives. In: Handbook of size exclusion chromatography. Marcel Dekker Inc., New York, pp 331–352
Cranston ED, Gray DG (2006) Morphological and optical characterization of polyelectrolyte multilayers incorporating nanocrystalline cellulose. Biomacromol 7:2522–2530. https://doi.org/10.1021/bm0602886
D’Acierno F, Hamad WY, Michal CA, Maclachlan MJ (2020) Thermal degradation of cellulose filaments and nanocrystals. Biomacromol 21:3374–3386. https://doi.org/10.1021/acs.biomac.0c00805
Delepierre G, Vanderfleet OM, Niinivaara E, et al (2021) Benchmarking cellulose nanocrystals part II: new industrially produced materials. Langmuir la-2021-00550w
Dong XM, Gray DG (1997) Effect of counterions on ordered phase formation in suspensions of charged rodlike cellulose crystallites. Langmuir 13:2404–2409. https://doi.org/10.1021/la960724h
Evans R, Wearne RH, Adrian FA (1989) Molecular weight distribution of cellulose as its tricarbanilate by high performance size exclusion chromatography. J Appl Polym Sci 37:3291–3303
Foster EJ, Moon RJ, Agarwal UP et al (2018) Current characterization methods for cellulose nanomaterials. Chem Soc Rev 47:2609–2679. https://doi.org/10.1039/c6cs00895j
Fujisawa S, Okita Y, Fukuzumi H et al (2011) Preparation and characterization of TEMPO-oxidized cellulose nanofibril films with free carboxyl groups. Carbohydr Polym 84:579–583. https://doi.org/10.1016/j.carbpol.2010.12.029
Fukuzumi H, Saito T, Okita Y, Isogai A (2010) Thermal stabilization of TEMPO-oxidized cellulose. Polym Degrad Stab 95:1502–1508. https://doi.org/10.1016/j.polymdegradstab.2010.06.015
Fukuzumi H, Fujisawa S, Saito T, Isogai A (2013) Selective permeation of hydrogen gas using cellulose nanofibril film. Biomacromol 14:1705–1709. https://doi.org/10.1021/bm400377e
Gurgel LVA, Marabezi K, Zanbom MD, Curvelo AADS (2012) Dilute acid hydrolysis of sugar cane bagasse at high temperatures: a kinetic study of cellulose saccharification and glucose decomposition. Part I: sulfuric acid as the catalyst. Ind Eng Chem Res 51:1173–1185. https://doi.org/10.1021/ie2025739
Heggset EB, Chinga-Carrasco G, Syverud K (2017) Temperature stability of nanocellulose dispersions. Carbohydr Polym 157:114–121. https://doi.org/10.1016/j.carbpol.2016.09.077
Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–85. https://doi.org/10.1039/c0nr00583e
Jiang F, Hsieh YL (2016) Self-assembling of TEMPO oxidized cellulose nanofibrils as affected by protonation of surface carboxyls and drying methods. ACS Sustain Chem Eng 4:1041–1049. https://doi.org/10.1021/acssuschemeng.5b01123
Kargarzadeh H, Ahmad I, Abdullah I et al (2012) Effects of hydrolysis conditions on the morphology, crystallinity, and thermal stability of cellulose nanocrystals extracted from kenaf bast fibers. Cellulose 19:855–866. https://doi.org/10.1007/s10570-012-9684-6
Khodayari A, Hirn U, Spirk S et al (2021) Recrystallization and size distribution of dislocated segments in cellulose microfibrils—a molecular dynamics perspective. Cellulose 28:6007–6022. https://doi.org/10.1007/s10570-021-03906-7
Kloser E, Gray DG (2010) Surface grafting of cellulose nanocrystals with poly(ethylene oxide) in aqueous media. Langmuir 26:13450–13456. https://doi.org/10.1021/la101795s
Leung ACW, Hrapovic S, Lam E et al (2011) Characteristics and properties of carboxylated cellulose nanocrystals prepared from a novel one-step procedure. Small 7:302–305. https://doi.org/10.1002/smll.201001715
Lewis L, Derakhshandeh M, Hatzikiriakos SG et al (2016) Hydrothermal gelation of aqueous cellulose nanocrystal suspensions. Biomacromol 17:2747–2754. https://doi.org/10.1021/acs.biomac.6b00906
Lichtenstein K, Lavoine N (2017) Toward a deeper understanding of the thermal degradation mechanism of nanocellulose. Polym Degrad Stab 146:53–60. https://doi.org/10.1016/j.polymdegradstab.2017.09.018
Lin N, Dufresne A (2014) Surface chemistry, morphological analysis and properties of cellulose nanocrystals with gradiented sulfation degrees. Nanoscale 6:5384–5393. https://doi.org/10.1039/c3nr06761k
Lu P, Hsieh YL (2012) Preparation and characterization of cellulose nanocrystals from rice straw. Carbohydr Polym 87:564–573. https://doi.org/10.1016/j.carbpol.2011.08.022
Marchessault RH, Morehead FF, Koch MJ (1961) Some hydrodynamic properties of neutral as related to size and shape 1. J Colloid Sci 344:327–344
Matsuoka S, Kawamoto H, Saka S (2014) What is active cellulose in pyrolysis? An approach based on reactivity of cellulose reducing end. J Anal Appl Pyrol 106:138–146. https://doi.org/10.1016/j.jaap.2014.01.011
McAlpine S, Nakoneshny J (2019) Production of crystalline cellulose
Molnes SN, Paso KG, Strand S, Syverud K (2017) The effects of pH, time and temperature on the stability and viscosity of cellulose nanocrystal (CNC) dispersions: implications for use in enhanced oil recovery. Cellulose. https://doi.org/10.1007/s10570-017-1437-0
Molnes SN, Mamonov A, Paso KG et al (2018) Investigation of a new application for cellulose nanocrystals: a study of the enhanced oil recovery potential by use of a green additive. Cellulose 25:2289–2301. https://doi.org/10.1007/s10570-018-1715-5
Nickerson RF, Habrle JA (1947) Cellulose intercrystalline structure. Ind Eng Chem 39:1507–1512. https://doi.org/10.1021/ie50455a024
Nishiyama Y, Langan P, Chanzy H (2002) Crystal structure and hydrogen-bonding system in cellulose Iβ from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 124:9074–9082. https://doi.org/10.1021/ja0257319
Nishiyama Y, Kim UJ, Kim DY et al (2003) Periodic disorder along ramie cellulose microfibrils. Biomacromol 4:1013–1017. https://doi.org/10.1021/bm025772x
Rånby BG (1951) The colloidal properties of cellulose micelles. Discuss Faraday Soc 11:158–164
Rånby BG, Banderet A, Sillén LG (1949) Aqueous colloidal solutions of cellulose micelles. Acta Chem Scand 3:649–650. https://doi.org/10.3891/acta.chem.scand.03-0649
Reid MS, Villalobos M, Cranston ED (2017) Benchmarking cellulose nanocrystals: from the laboratory to industrial production. Langmuir 33:1583–1598. https://doi.org/10.1021/acs.langmuir.6b03765
Revol J-F, Bradford H, Giasson J et al (1992) Helicoidal self-ordering of cellulose microfibrils in aqueous suspension. Int J Biol Macromol 14:170–172. https://doi.org/10.1016/S0141-8130(05)80008-X
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+
Saha S, Hemraz UD, Boluk Y (2020) The effects of high pressure and high temperature in semidilute aqueous cellulose nanocrystal suspensions. Biomacromol 21:1031–1035. https://doi.org/10.1021/acs.biomac.9b01130
Shafiei-Sabet S, Hamad WY, Hatzikiriakos SG (2014) Ionic strength effects on the microstructure and shear rheology of cellulose nanocrystal suspensions. Cellulose 21:3347–3359. https://doi.org/10.1007/s10570-014-0407-z
Silveira RL, Stoyanov SR, Kovalenko A, Skaf MS (2016) Cellulose aggregation under hydrothermal pretreatment conditions. Biomacromol 17:2582–2590. https://doi.org/10.1021/acs.biomac.6b00603
Stålbrand H, Mansfield SD, Saddler JN et al (1998) Analysis of molecular size distributions of cellulose molecules during hydrolysis of cellulose by recombinant Cellulomonas fimi beta-1,4-glucanases. Appl Environ Microbiol 64:2374–2379
Suchy M, Vuorinen T, Kontturi E (2010) Thermal degradation of cellulose nanocrystals deposited on different surfaces. Macromol Symp 294:51–57. https://doi.org/10.1002/masy.200900031
Takaichi S, Saito T, Tanaka R, Isogai A (2014) Improvement of nanodispersibility of oven-dried TEMPO-oxidized celluloses in water. Cellulose 21:4093–4103. https://doi.org/10.1007/s10570-014-0444-7
Uhlig M, Fall A, Wellert S et al (2016) Two-dimensional aggregation and semidilute ordering in cellulose nanocrystals. Langmuir 32:442–450. https://doi.org/10.1021/acs.langmuir.5b04008
Van De Ven TGM, Sheikhi A (2016) Hairy cellulose nanocrystalloids: a novel class of nanocellulose. Nanoscale 8:15101–15114. https://doi.org/10.1039/c6nr01570k
Vanderfleet OM, Cranston ED (2020) Production routes to tailor the performance of cellulose nanocrystals. Nat Rev Mater. https://doi.org/10.1038/s41578-020-00239-y
Vanderfleet OM, Reid MS, Bras J et al (2019) Insight into thermal stability of cellulose nanocrystals from new hydrolysis methods with acid blends. Cellulose 26:507–528. https://doi.org/10.1007/s10570-018-2175-7
Viet D, Beck-Candanedo S, Gray DG (2007) Dispersion of cellulose nanocrystals in polar organic solvents. Cellulose 14:109–113. https://doi.org/10.1007/s10570-006-9093-9
Wang Q, Zhao X, Zhu JY (2014) Kinetics of strong acid hydrolysis of a bleached kraft pulp for producing cellulose nanocrystals (CNCs). Ind Eng Chem Res 53:11007–11014. https://doi.org/10.1021/ie501672m
Xu Y, Atrens AD, Stokes JR (2017) Rheology and microstructure of aqueous suspensions of nanocrystalline cellulose rods. J Colloid Interface Sci 496:130–140. https://doi.org/10.1016/j.jcis.2017.02.020
Yang H, Chen D, van de Ven TGM (2015) Preparation and characterization of sterically stabilized nanocrystalline cellulose obtained by periodate oxidation of cellulose fibers. Cellulose 22:1743–1752. https://doi.org/10.1007/s10570-015-0584-4
Yu HY, Zhang DZ, Lu FF, Yao J (2016) New approach for single-step extraction of carboxylated cellulose nanocrystals for their use as adsorbents and flocculants. ACS Sustain Chem Eng 4:2632–2643. https://doi.org/10.1021/acssuschemeng.6b00126
Zhou Y, Saito T, Bergström L, Isogai A (2018) Acid-free preparation of cellulose nanocrystals by TEMPO oxidation and subsequent cavitation. Biomacromol 19:633–639. https://doi.org/10.1021/acs.biomac.7b01730
Acknowledgments
The authors acknowledge Professors Scott Renneckar and Feng Jiang for equipment usage, as well as Maureen Fitzpatrick and Victoria Jarvis (at McMaster University) for X-ray diffraction expertise.
Funding
The authors acknowledge research funding from Canada’s Natural Sciences and Engineering Research Council (including Canada Graduate Scholarships, Undergraduate Student Research Award, Michael Smith Foreign Study Supplement, and NSERC Discovery Grant RGPIN-2017–05252) and Mitacs (Globalink Research Award). LGP2 is part of the LabEx Tec 21 (Investissements d’Avenir—Grant Agreement No. ANR-11-LABX-0030) and of PolyNat Carnot Institute (Investissements d’Avenir—Grant Agreement No. ANR-16-CARN-0025–01).
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Vanderfleet, O.M., Winitsky, J., Bras, J. et al. Hydrothermal treatments of aqueous cellulose nanocrystal suspensions: effects on structure and surface charge content. Cellulose 28, 10239–10257 (2021). https://doi.org/10.1007/s10570-021-04187-w
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DOI: https://doi.org/10.1007/s10570-021-04187-w