, Volume 26, Issue 5, pp 2941–2954 | Cite as

Cellulose consolidation under high-pressure and high-temperature uniaxial compression

  • Thibaud Pintiaux
  • Maelie Heuls
  • Virginie Vandenbossche
  • Timothy Murphy
  • Richard Wuhrer
  • Patrice Castignolles
  • Marianne GaborieauEmail author
  • Antoine Rouilly
Original Research


Materials based on cellulose cannot be obtained from thermoplastic processes. Our aim is to prepare all-cellulose materials by uniaxial high pressure thermocompression of cellulose. The effect of moisture content (0–8 w/w%) and temperature (175–250 °C) was characterized through the mechanical properties (bending and tensile), morphology (scanning electron microscopy, X-ray tomography) and microstructure (viscometric degree of polymerization, Raman spectroscopy, X-ray diffraction, solid-state NMR) of the specimens. The specimens were mechanically stronger in bending than in tension. They exhibited a more porous heart, a dense but very thin skin on the faces (orthogonal to the compression axis) and thick and extremely dense sides. During thermocompression severe friction between fibers caused a decrease in molecular weight while heating above the glass transition temperature was responsible for water migration towards the specimen heart. Most of the cohesion came from the small sides of the test samples (parallel to the compression axis) and seemed mainly related to the entanglement of amorphized cellulose at the interface between particles. Around 200 °C water accumulated and provoked delamination upon pressure release, but at higher temperatures water, in a subcritical state, may have been consumed during the hydrolysis of amorphous cellulose regions. The all-cellulose material with the best mechanical properties was obtained at 2% moisture and 250 °C. This work shows that thermocompression at high temperature with limited moisture may be viable to produce renewable, sustainable all-cellulose materials for application in biobased plastic substitutes including binderless boards.

Graphical abstract


All-cellulose materials Compression Mechanical properties 



The French National Research Agency (ANR) and the Competitive Cluster for the Agricultural and Food Industries in South-West France (AGRIMIP) financed this study under the aegis of the HYPMOBB (High Pressure Molding of Biopolymers and Biocomposites) project. PC thanks the Academic Development Program at WSU for his stay at INP Toulouse. The authors are grateful to Brigitte Dubreuil and Manuel Marcoux for their precious help with Raman spectroscopy and X-ray tomography, respectively. The authors thank the Advanced Materials Characterisation Facility (AMFC) at Western Sydney University (WSU) for the use of the X-ray diffractometer and the scanning electron microscope (SEM), Matthew Van Leeuwen (WSU) for discussions on deconvolution of XRD data, as well as the School of Science and Health (WSU), and Dr James Hook, Dr Aditya Rawal (Mark Wainwright Analytical Centre, University of New South Wales) for the use of solid-state NMR spectrometers. MH thanks Conseil Régional Midi-Pyrénées for financial help for her stay at WSU.

Supplementary material

10570_2019_2273_MOESM1_ESM.pdf (888 kb)
Supplementary material 1 (PDF 888 kb)


  1. Agarwal UP, Reiner RS, Ralph SA (2010) Cellulose I crystallinity determination using FT–Raman spectroscopy: univariate and multivariate methods. Cellulose 17:721–733CrossRefGoogle Scholar
  2. Busignies V, Leclerc B, Porion P, Evesque P, Couarraze G, Tchoreloff P (2006) Quantitative measurements of localized density variations in cylindrical tablets using X-ray microtomography. Eur J Pharm Biopharm 64:38–50CrossRefPubMedGoogle Scholar
  3. Ciolacu D, Ciolacu F, Popa VI (2011) Amorphous cellulose—structure and characterization. Cellul Chem Technol 45:13–21Google Scholar
  4. French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896CrossRefGoogle Scholar
  5. French AD, Bertoniere NR, Brown RM, Chanzy H, Gray D, Hattori K, Glasser W (2000) Cellulose. Kirk-Othmer Encyclopedia of Chemical Technology. Wiley, New York. CrossRefGoogle Scholar
  6. Gidley MJ, Robinson G (1990) Techniques for studying interactions between polysaccharides, (Chapter 18). In: Dey PM, Harborne JB (eds) Methods in Plant Biochemistry, vol 2 Carbohydrates. Academic Press, Cambidge, pp 607–642CrossRefGoogle Scholar
  7. Huber T, Müssig J, Curnow O, Pang S, Bickerton S, Staiger MP (2012) A critical review of all-cellulose composites. J Mater Sci 47:1171–1186CrossRefGoogle Scholar
  8. Jallabert B, Vaca-Medina G, Cazalbou S, Rouilly A (2013) The pressure-volume-temperature relationship of cellulose. Cellulose 20:2279–2289CrossRefGoogle Scholar
  9. Kargin PV, Kozlov VA, Van NC (1960) Classification temperature of cellulose. Dokl Akad Nauk SSSR 130:356–358Google Scholar
  10. Kumar V, Kothari SH (1999) Effect of compressional force on the crystallinity of directly compressible cellulose excipients. Int J Pharm 177:173–182CrossRefPubMedGoogle Scholar
  11. Michrafy A, Ringenbacher D, Tchoreloff P (2002) Modelling the compaction behaviour of powders: application to pharmaceutical powders. Powder Technol 127:257–266CrossRefGoogle Scholar
  12. Nam S, French AD, Condon BD, Concha M (2016) Segal crystallinity index revisited by the simulation of X-ray diffraction patterns of cotton cellulose Iβ and cellulose II. Carbohydr Polym 135:1–9CrossRefPubMedGoogle Scholar
  13. Nonaka S, Umemura K, Kawai S (2012) Characterization of bagasse binderless particleboard manufactured in high-temperature range. J Wood Sci 59:50–56CrossRefGoogle Scholar
  14. Obradovic J, Wondraczek H, Fardim P, Lassila L, Navard P (2014) Preparation of three-dimensional cellulose objects previously swollen in a DMAc/LiCl solvent system. Cellulose 21:4029–4038CrossRefGoogle Scholar
  15. Ogiwara Y, Kubota H, Hayashi S, Mitomo N (1970) Temperature dependency of bound water of cellulose studied by a high-resolution NMR spectrometer. J Appl Polym Sci 14:303–309CrossRefGoogle Scholar
  16. Paes SS, Sun S, MacNaughtan W, Ibbett R, Ganster J, Foster TJ, Mitchell JR (2010) The glass transition and crystallization of ball milled cellulose. Cellulose 17:693–709CrossRefGoogle Scholar
  17. Park S, Baker JO, Himmel ME, Parilla PA, Johnson DK (2010) Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance. Biotechnol Biofuels 3:10CrossRefPubMedPubMedCentralGoogle Scholar
  18. Pintiaux T, Viet D, Vandenbossche V, Rigal L, Rouilly A (2013) High pressure compression-molding of alpha-cellulose and effects of operating conditions. Materials 6:2240–2261CrossRefPubMedPubMedCentralGoogle Scholar
  19. Pintiaux T, Viet D, Vandenbossche V, Rigal L, Rouilly A (2015a) Binderless materials obtained by thermo-compressive processing of lignocellulosic fibers: a comprehensive review. BioResources 10:1915–1963CrossRefGoogle Scholar
  20. Pintiaux T, Laourine F, Vacamedina G, Rouilly A, Peydecastaing J (2015b) Hydrophobic cellulose-based materials obtained by uniaxial high pressure compression: in situ esterification with fatty acids and fatty anhydrides. BioResources 10:4626–4640CrossRefGoogle Scholar
  21. Privas E, Felder E, Navard P (2013) Destructuration of cotton under elevated pressure. Cellulose 20:1001–1011CrossRefGoogle Scholar
  22. Pu Y, Hallac B, Ragauskas AJ (2013) Plant biomass characterization: application of solution- and solid-state NMR spectroscopy (Chapter 18). In: Wymann CE (ed) Aqueous pretreatment of plant biomass for biological and chemical conversion to fuels and chemicals. Wiley, Chichester, pp 369–390. CrossRefGoogle Scholar
  23. Rebière J, Heuls M, Castignolles P, Gaborieau M, Rouilly A, Violleau F, Durrieu V (2016) Structural modifications of cellulose samples after dissolution into various solvent systems. Anal Bioanal Chem 408:8403–8414CrossRefPubMedGoogle Scholar
  24. Rouilly A, Rigal L (2002) Agro-materials: a bibliographic review. J Macromol Sci Polym Rev C42:441–479CrossRefGoogle Scholar
  25. Sasaki M, Adschiri T, Arai K (2004) Kinetics of cellulose conversion at 25 MPa in sub- and supercritical water. AIChE J 50:192–202CrossRefGoogle Scholar
  26. Schroeter J, Felix F (2005) Melting cellulose. Cellulose 12:159–165CrossRefGoogle Scholar
  27. Siró I, Plackett D (2010) Microfibrillated cellulose and new nanocomposite materials: a review. Cellulose 17:459–494CrossRefGoogle Scholar
  28. Szcześniak L, Rachocki A, Tritt-Goc J (2007) Glass transition temperature and thermal decomposition of cellulose powder. Cellulose 15:445–451CrossRefGoogle Scholar
  29. Thoorens G, Krier F, Leclercq B, Carlin B, Evrard B (2014) Microcrystalline cellulose, a direct compression binder in a quality by design environment—a review. Int J Pharm 473:64–72CrossRefPubMedGoogle Scholar
  30. Vaca-Medina G, Jallabert B, Viet D, Peydecastaing J, Rouilly A (2013) Effect of temperature on high pressure cellulose compression. Cellulose 20:2311–2319CrossRefGoogle Scholar
  31. Zhang X, Wu X, Gao D, Xia K (2012) Bulk cellulose plastic materials from processing cellulose powder using back pressure-equal channel angular pressing. Carbohydr Polym 87:2470–2476CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Laboratoire de Chimie Agro-industrielle (LCA)Université de Toulouse, INRA, INPTToulouseFrance
  2. 2.Medical Sciences Research Group, School of Science and HealthWestern Sydney UniversityParramattaAustralia
  3. 3.Australian Centre for Research on Separation Science (ACROSS), School of Science and HealthWestern Sydney UniversityPenrithAustralia
  4. 4.Advanced Materials Characterisation Facility (AMCF)Western Sydney UniversityParramattaAustralia

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