, Volume 25, Issue 1, pp 87–104 | Cite as

Changes in the hygroscopic behavior of cellulose due to variations in relative humidity

  • Ville A. LovikkaEmail author
  • Lauri Rautkari
  • Thaddeus C. Maloney
Original Paper


Details on how cellulosic surfaces change under changing moisture are incomplete and even existing results are occasionally neglected. Unlike sometimes reported, water adsorption is unsuitable for surface area measurements. However, water can be utilized for assessing surface dynamics. Hygroscopic changes of pulp and bacterial cellulose were studied by dehydrating the samples in a low polarity solvent and then introducing them into a moist atmosphere in a dynamic vapor sorption (DVS) apparatus at 0–93% relative humidity (RH). The DVS treatment caused hygroscopicity loss near applied RH maxima, however, the hygroscopicity increased at RH values > 10–20% units lower. Additionally, the hygroscopic changes were partially reversible near the RH maximum. Therefore the hygroscopicity of cellulose could be controlled by tailoring the exposure history of the sample. Hornification reduced these changes. The observations support reported molecular simulations where cellulose was shown to restructure its surface depending on the polarity of its environment.


Cellulose Water adsorption Solvent exchange Hornification Surface restructuring Critical point drying 



This work was a part of ACel program of the Finnish Bioeconomy Cluster FIBIC. The funding of the Finnish Funding Agency for Technology and Innovation (TEKES) and the Academy of Finland (POROFIBRE Project) is acknowledged. Katarina Dimic-Misic is thanked for providing the BC. Benjamin Wilson is thanked for proofreading. Henna Penttinen is thanked for the initial literature review in her interesting undergraduate thesis on cellulose surfaces in environments with different polarities. This work made use of the Aalto University Nanomicroscopy Center (Aalto-NMC) premises.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. Atalla RH, Brady JW, Matthews JF, Ding S-Y and Himmel ME (2008) Structures of plant cell wall celluloses. In: Biomass recalcitrance. Blackwell Publishing Ltd.
  2. Banik G, Brückle I (2010) Principles of water absorption and desorption in cellulosic materials. Restaurator 31:164–177. Google Scholar
  3. Bazooyar F, Bohlén M, Bolton K (2015) Computational studies of water and carbon dioxide interactions with cellobiose. J Mol Model 21:16. CrossRefGoogle Scholar
  4. Belbekhouche S, Bras J, Siqueira G, Chappey C, Lebrun L, Khelifi B, Marais S, Dufresne A (2011) Water sorption behavior and gas barrier properties of cellulose whiskers and microfibrils films. Carbohydr Polym 83:1740–1748. CrossRefGoogle Scholar
  5. Berthold J, Rinaudo M, Salmén L (1996) Association of water to polar groups; estimations by an adsorption model for ligno-cellulosic materials. Colloids Surf A 112:117–129. CrossRefGoogle Scholar
  6. Bledzki AK, Gassan J (1999) Composites reinforced with cellulose based fibres. Prog Polym Sci 24:221–274. CrossRefGoogle Scholar
  7. Brunauer S, Emmett PH, Teller E (1938) Adsorption of gases in multimolecular layers. J Am Chem Soc 60:309–319. CrossRefGoogle Scholar
  8. Castro C, Zuluaga R, Álvarez C, Putaux JL, Caro G, Rojas OJ, Mondragon I, Gañán P (2012) Bacterial cellulose produced by a new acid-resistant strain of Gluconacetobacter genus. Carbohydr Polym 89:1033–1037. CrossRefGoogle Scholar
  9. Caurie M (2012) A method to correct the wide discrepancy between Brunauer, Emmett and Teller water and N2 surface areas of adsorbents. Int J Food Sci Technol 47:2366–2371. CrossRefGoogle Scholar
  10. Chirkova J, Andersons B, Andersone I (2009) Study of the structure of wood-related biopolymers by sorption methods. BioResources 4:1044–1057Google Scholar
  11. Christensen GN (1959) The rate of sorption of water vapor by wood and pulp. Appita J 13:112–123Google Scholar
  12. Cohan LH (1938) Sorption hysteresis and the vapor pressure of concave surfaces. J Am Chem Soc 60:433–435. CrossRefGoogle Scholar
  13. Driemeier C, Mendes FM, Oliveira MM (2012) Dynamic vapor sorption and thermoporometry to probe water in celluloses. Cellulose 19:1051–1063. CrossRefGoogle Scholar
  14. Dufresne A (2012) Cellulose and potential reinforcement. In: Nanocellulose—from nature to high performance tailored materials. Walter de Gruyter GmbH, pp 1–42Google Scholar
  15. Engelund ET, Thygesen LG, Svensson S, Hill CAS (2013) A critical discussion of the physics of wood–water interactions. Wood Sci Technol 47:141–161. CrossRefGoogle Scholar
  16. Espino-Pérez E, Bras J, Almeida G, Relkin P, Belgacem N, Plessis C, Domenek S (2016) Cellulose nanocrystal surface functionalization for the controlled sorption of water and organic vapours. Cellulose 23:2955–2970. CrossRefGoogle Scholar
  17. Fernandes Diniz JMB, Gil MH, Castro JAAM (2004) Hornification—its origin and interpretation in wood pulps. Wood Sci Technol 37:489–494. CrossRefGoogle Scholar
  18. Fernandes AN, Thomas LH, Altaner CM, Callow P, Forsyth VT, Apperley DC, Kennedy CJ, Jarvis MC (2011) Nanostructure of cellulose microfibrils in spruce wood. Proc Natl Acad Sci USA 108:1195–1203. CrossRefGoogle Scholar
  19. Glass SV, Boardman CR, Zelinka SL (2017) Short hold times in dynamic vapor sorption measurements mischaracterize the equilibrium moisture content of wood. Wood Sci Technol 51:243–260. CrossRefGoogle Scholar
  20. Grethlein HE (1985) The effect of pore size distribution on the rate of enzymatic hydrolysis of cellulosic substrates. Nat Biotechnol 3:155–160. CrossRefGoogle Scholar
  21. Greyson J, Levi AA (1963) Calorimetric measurements of the heat of sorption of water vapor on dry swollen cellulose. J Polym Sci Part A 1:3333–3342. Google Scholar
  22. Grunin LY, Grunin YB, Talantsev VI, Nikolskaya EA, Masas DS (2015) Features of the structural organization and sorption properties of cellulose. Polym Sci Ser A 57:43–51. CrossRefGoogle Scholar
  23. Häggkvist M, Li T-Q, Ödberg L (1998) Effects of drying and pressing on the pore structure in the cellulose fibre wall studied by 1H and 2H NMR relaxation. Cellulose 5:33–49. CrossRefGoogle Scholar
  24. Heiner AP, Kuutti L, Teleman O (1998) Comparison of the interface between water and four surfaces of native crystalline cellulose by molecular dynamics simulations. Carbohydr Res 306:205–220. CrossRefGoogle Scholar
  25. Hill CAS, Norton A, Newman G (2009) The water vapor sorption behavior of natural fibers. J Appl Polym Sci 112:1524–1537. CrossRefGoogle Scholar
  26. Hill CAS, Keating BA, Jalaludin Z, Mahrdt E (2012) A rheological description of the water vapour sorption kinetics behaviour of wood invoking a model using a canonical assembly of Kelvin-Voigt elements and a possible link with sorption hysteresis. Holzforschung 66:35–47. CrossRefGoogle Scholar
  27. Hubbe MA, Rojas OJ, Lucia LA, Sain M (2008) Cellulosic nanocomposites: a review. Bioresources 3:929–980Google Scholar
  28. Hult E, Larsson PT, Iversen T (2001) Cellulose fibril aggregation—an inherent property of kraft pulps. Polymer (Guildf) 42:3309–3314. CrossRefGoogle Scholar
  29. Ioelovich M, Leykin A (2011) Study of sorption properties of cellulose and its derivatives. BioResources 6:178–195Google Scholar
  30. Iwamoto S, Abe K, Yano H (2008) The effect of hemicelluloses on wood pulp nanofibrillation and nanofiber network characteristics. Biomacromol 9:1022–1026. CrossRefGoogle Scholar
  31. Jalaludin Z (2011) The water vapour sorption behaviour of wood. Edinburgh Napier UniversityGoogle Scholar
  32. Johansson L-S, Tammelin T, Campbell JM, Setälä H, Österberg M (2011) Experimental evidence on medium driven cellulose surface adaptation demonstrated using nanofibrillated cellulose. Soft Matter 7:10917. CrossRefGoogle Scholar
  33. Khanjani P, Väisänen S, Lovikka V, Nieminen K, Maloney T, Vuorinen T (2017) Assessing the reactivity of cellulose by oxidation with 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxo-piperidinium cation under mild conditions. Carbohydr Polym 176:293–298. CrossRefGoogle Scholar
  34. Klemm D, Philipp B, Heinze T, Heinze U, Wagenknecht W (1998) General considerations on structure and reactivity of cellulose. In: Comprehensive cellulose chemistry. Wiley-VCH Verlag GmbH & Co. KGaA, pp 9–29Google Scholar
  35. Klemm D, Schumann D, Udhardt U, Marsch S (2001) Bacterial synthesized cellulose—artificial blood vessels for microsurgery. Prog Polym Sci 26:1561–1603. CrossRefGoogle Scholar
  36. Kohler R, Alex R, Brielmann R, Ausperger B (2006) A new kinetic model for water sorption isotherms of cellulosic materials. Macromol Symp 244:89–96. CrossRefGoogle Scholar
  37. Köhnke T, Gatenholm P (2007) The effect of controlled glucuronoxylan adsorption on drying-induced strength loss of bleached softwood pulp. Nord Pulp Pap Res J 22:508–515. CrossRefGoogle Scholar
  38. Kulasinski K, Keten S, Churakov SV, Guyer R, Carmeliet J, Derome D (2014) Molecular mechanism of moisture-induced transition in amorphous cellulose. ACS Macro Lett 3:1037–1040. CrossRefGoogle Scholar
  39. Kulasinski K, Guyer R, Keten S, Derome D, Carmeliet J (2015) Impact of moisture adsorption on structure and physical properties of amorphous biopolymers. Macromolecules 48:2793–2800. CrossRefGoogle Scholar
  40. Kulasinski K, Derome D, Carmeliet J (2017) Impact of hydration on the micromechanical properties of the polymer composite structure of wood investigated with atomistic simulations. J Mech Phys Solids 103:221–235. CrossRefGoogle Scholar
  41. Kymäläinen M, Havimo M, Louhelainen J (2014) Sorption properties of torrefied wood and charcoal. Wood Mater Sci Eng 9:170–178. CrossRefGoogle Scholar
  42. Lang ARG, Mason SG (1960) Tritium exchange between cellulose and water: accessibility measurements and effects of cyclic drying. Can J Chem 38:373–387. CrossRefGoogle Scholar
  43. Leppänen K, Andersson S, Torkkeli M, Knaapila M, Kotelnikova N, Serimaa R (2009) Structure of cellulose and microcrystalline cellulose from various wood species, cotton and flax studied by X-ray scattering. Cellulose 16:999–1015. CrossRefGoogle Scholar
  44. Leuk P, Schneeberger M, Hirn U, Bauer W (2015) Heat of sorption: a comparison between isotherm models and calorimeter measurements of wood pulp. Dry Technol 34:563–573. CrossRefGoogle Scholar
  45. Liao R, Zhu M, Xin Zhou, Zhang F, Yan J, Zhu W, Gu C (2012) Molecular dynamics study of the disruption of H-bonds by water molecules and its diffusion behavior in amorphous cellulose. Mod Phys Lett B 26:1250088. CrossRefGoogle Scholar
  46. Lovikka VA, Khanjani P, Väisänen S, Vuorinen T, Maloney TC (2016) Porosity of wood pulp fibers in the wet and highly open dry state. Microporous Mesoporous Mater 234:326–335. CrossRefGoogle Scholar
  47. Matthews JF, Skopec CE, Mason PE, Zuccato P, Torget RW, Sugiyama J, Himmel ME, Brady JW (2006) Computer simulation studies of microcrystalline cellulose Iβ. Carbohydr Res 341:138–152. CrossRefGoogle Scholar
  48. Maurer RJ, Sax AF, Ribitsch V (2013) Molecular simulation of surface reorganization and wetting in crystalline cellulose I and II. Cellulose 20:25–42. CrossRefGoogle Scholar
  49. Mazeau K (2015) The hygroscopic power of amorphous cellulose: a modeling study. Carbohydr Polym 117:585–591. CrossRefGoogle Scholar
  50. Medronho B, Duarte H, Alves L, Antunes F, Romano A, Lindman B (2015) Probing cellulose amphiphilicity. Nord Pulp Pap Res J 30:58–66. CrossRefGoogle Scholar
  51. Mihranyan A, Llagostera AP, Karmhag R, Strømme M, Ek R (2004) Moisture sorption by cellulose powders of varying crystallinity. Int J Pharm 269:433–442. CrossRefGoogle Scholar
  52. Minor JL (1994) Hornification—its origin and meaning. Prog Pap Recycl 3:93–95Google Scholar
  53. Mohan T, Spirk S, Kargl R, Doliška A, Vesel A, Salzmann I, Resel R, Ribitsch V, Stana-Kleinschek K (2012) Exploring the rearrangement of amorphous cellulose model thin films upon heat treatment. Soft Matter 8:9807–9815. CrossRefGoogle Scholar
  54. Nelson R, Oliver DW (1971) Study of cellulose structure and its relation to reactivity. J Polym Sci Polym Symp 36:305–320. CrossRefGoogle Scholar
  55. Newman RH (2004) Carbon-13 NMR evidence for cocrystallization of cellulose as a mechanism for hornification of bleached kraft pulp. Cellulose 11:45–52. CrossRefGoogle Scholar
  56. Newns AC (1973) Sorption and Desorption Kinetics of the Cellulose and Water System - Part 2. J Chem Soc, Faraday Trans 1(69):444–448. CrossRefGoogle Scholar
  57. Oksanen T, Buchert J, Viikari L (1997) The role of hemiocelluloses in the hornification of bleached kraft pulps. Holzforschung 51:355–360. CrossRefGoogle Scholar
  58. Olsson A-M, Salmén L (2004) The association of water to cellulose and hemicellulose in paper examined by FTIR spectroscopy. Carbohydr Res 339:813–818. CrossRefGoogle Scholar
  59. Pierce C, Wiley JW, Smith RN (1949) Capillarity and surface area of charcoal. J Phys Chem 53:669–683. CrossRefGoogle Scholar
  60. Robens E, Dąbrowski A, Kutarov VV (2004) Comments on surface structure analysis by water and nitrogen adsorption. J Therm Anal Calorim 76:647–657. CrossRefGoogle Scholar
  61. Rowen JW, Blaine RL (1947) Sorption of nitrogen and water vapor on textile fibers. Ind Eng Chem 39:1659–1663. CrossRefGoogle Scholar
  62. Salmén L (1982) Temperature and water induced softening behaviour of wood fiber based materials. The Royal Institute of Technology, StockholmGoogle Scholar
  63. Salmén L, Bergström E (2009) Cellulose structural arrangement in relation to spectral changes in tensile loading FTIR. Cellulose 16:975–82. doi: 10.1007/s10570-009-9331-z CrossRefGoogle Scholar
  64. Sepall O, Mason SG (1961) Hydrogen exchange between cellulose and water: II. Interconversion of accessible and inaccessible regions. Can J Chem 39:1944–1955. CrossRefGoogle Scholar
  65. Sing KSW (2014) Assessment of surface area by gas adsorption. In: Adsorption by powders and porous solids, 2nd edn. Elsevier Ltd., Amsterdam, pp 237–68Google Scholar
  66. Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquérol J, Siemieniewska T (1985) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure Appl Chem 57:603–619. CrossRefGoogle Scholar
  67. Sinko R, Qin X, Keten S (2015) Interfacial mechanics of cellulose nanocrystals. MRS Bull 40:340–348. CrossRefGoogle Scholar
  68. Siró I, Plackett D (2010) Microfibrillated cellulose and new nanocomposite materials: a review. Cellulose 17:459–494. CrossRefGoogle Scholar
  69. Stone JE, Scallan AM (1966) Influence of drying on the pore structures of the cell wall. In: Consolidation of the paper web: transactions of the symposium held at Cambridge, pp 145–174Google Scholar
  70. Stone JE, Scallan AM (1967) The effect of component removal upon the porous structure of the cell wall of wood. II. Swelling in water and the fiber saturation point. Tappi J 50:496–501Google Scholar
  71. Strømme M, Mihranyan A, Ek R, Niklasson GA (2003) Fractal dimension of cellulose powders analyzed by multilayer BET adsorption of water and nitrogen. J Phys Chem B 107:14378–14382. CrossRefGoogle Scholar
  72. Suchy M, Kontturi E, Vuorinen T (2010a) Impact of drying on wood ultrastructure: similarities in cell wall alteration between native wood and isolated wood-based fibers. Biomacromolecules 11:2161–2168. CrossRefGoogle Scholar
  73. Suchy M, Virtanen J, Kontturi E, Vuorinen T (2010b) Impact of drying on wood ultrastructure observed by deuterium exchange and photoacoustic FT-IR spectroscopy. Biomacromolecules 11:515–520. CrossRefGoogle Scholar
  74. Taniguchi T, Harada H, Nakato K (1978) Determination of water adsorption sites in wood by a hydrogen–deuterium exchange. Nature 272:230–231. CrossRefGoogle Scholar
  75. Thybring EE, Thygesen LG, Burgert I (2017) Hydroxyl accessibility in wood cell walls as affected by drying and re-wetting procedures. Cellulose 24:2375–2384. CrossRefGoogle Scholar
  76. Timmermann EO (2003) Multilayer sorption parameters: BET or GAB values? Colloids Surf A 220:235–260. CrossRefGoogle Scholar
  77. Topgaard D, Söderman O (2001) Diffusion of water absorbed in cellulose fibers studied with 1 H-NMR. Langmuir 17:2694–2702. CrossRefGoogle Scholar
  78. Weatherwax RC (1977) Collapse of cell-wall pores during drying of cellulose. J Colloid Interface Sci 62:432–446. CrossRefGoogle Scholar
  79. Weatherwax RC, Caulfield DF (1971) Cellulose aerogels: an improved method for preparing a highly expanded form of dry cellulose. Tappi J 54:985–986Google Scholar
  80. Weise U, Maloney T, Paulapuro H (1996) Quantification of water in different states of interaction with wood pulp fibres. Cellulose 3:189–202. CrossRefGoogle Scholar
  81. Willems W (2014a) The water vapor sorption mechanism and its hysteresis in wood: the water/void mixture postulate. Wood Sci Technol 48:499–518. CrossRefGoogle Scholar
  82. Willems W (2014b) Hydrostatic pressure and temperature dependence of wood moisture sorption isotherms. Wood Sci Technol 48:483–498. CrossRefGoogle Scholar
  83. Xie Y, Hill CAS, Jalaludin Z, Curling SF, Anandjiwala RD, Norton AJ, Newman G (2010) The dynamic water vapour sorption behaviour of natural fibres and kinetic analysis using the parallel exponential kinetics model. J Mater Sci 46:479–489. CrossRefGoogle Scholar
  84. Xie Y, Hill CAS, Jalaludin Z, Sun D (2011) The water vapour sorption behaviour of three celluloses: analysis using parallel exponential kinetics and interpretation using the Kelvin-Voigt viscoelastic model. Cellulose 18:517–530. CrossRefGoogle Scholar
  85. Yamane C, Aoyagi T, Ago M, Sato K, Okajima K, Takahashi T (2006) Two different surface properties of regenerated cellulose due to structural anisotropy. Polym J 38:819–826. CrossRefGoogle Scholar
  86. Zheng Y, Lin H, Tsao GT (1998) Pretreatment for cellulose hydrolysis by carbon dioxide explosion. Biotechnol Prog 14:890–896. CrossRefGoogle Scholar
  87. Zografi G, Kontny MJ (1986) The interactions of water with cellulose- and starch-derived pharmaceutical excipients. Pharm Res 3:187–194. CrossRefGoogle Scholar
  88. Zografi G, Kontny MJ, Yang AYS, Brenner GS (1984) Surface area and water vapor sorption of microcrystalline cellulose. Int J Pharm 18:99–116. CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V., part of Springer Nature 2017

Authors and Affiliations

  1. 1.Department of Forest Products Technology, School of Chemical TechnologyAalto UniversityAaltoFinland
  2. 2.Department of ChemistryUniversity of HelsinkiHelsinkiFinland

Personalised recommendations