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Licensed Unlicensed Requires Authentication Published by De Gruyter July 17, 2014

Material pocket dynamic mechanical analysis: a novel tool to study thermal transition in wood fibers plasticized by an ionic liquid (IL)

  • Rongxian Ou , Yanjun Xie , Qingwen Wang EMAIL logo , Shujuan Sui and Michael P. Wolcott EMAIL logo
From the journal Holzforschung


The investigation of phase transition in powdered materials by dynamic mechanical analysis (DMA) is not straightforward because powders are difficult to prepare in a solid compact form without altering their structure and properties. In this study, a material pocket (MP) method has been applied to provide physical support to powdered samples for DMA testing (MP-DMA). Poplar wood strips and four types of wood particles [native wood flour (WF), α-cellulose (αC), holocellulose (HC), and particles without hemicelluloses (HR)] were treated with an ionic liquid (IL), 1-ethyl-3-methylimidazolium chloride ([Emim]Cl), to a weight percent gain (WPG) of 36%. Results show that all four [Emim]Cl-treated wood particles exhibited three apparent transition peaks over the measured temperature range. Paracrystalline cellulose, hemicelluloses, and lignin all exhibited a glass transition temperature (Tg) at approximately 85°C due to the plasticizing effect of [Emim]Cl. The transition peak at a higher temperature may be due to the melting of crystalline cellulose in [Emim]Cl. MP-DMA is an effective tool for direct monitoring the phase transition of powdered lignocellulosics. This provides new insight into the interactions of ILs and cell wall polymers, and the method established can be easily extended to other systems based on powdered samples.

Corresponding authors: Qingwen Wang, Key Laboratory of Bio-Based Material Science and Technology (Ministry of Education), Northeast Forestry University, Harbin 150040, China, Tel/Fax: +8645182191993, e-mail: ; and Michael P. Wolcott, Composite Materials and Engineering Center, Washington State University, Pullman, WA 99164, USA, Tel.: +1 509 335 6392, Fax: +1 509 335 5077, e-mail:


The supports from the Special Funds for Scientific Research on Public Causes of Forestry (No. 201204802) are gratefully acknowledged. Yanjun Xie thanks the Program for New Century Excellent Talents in the University of Ministry of Education of China (No. NCET-11-0608).


Abiad, M.G., Campanella, O.H., Carvajal, M.T. (2010) Assessment of thermal transitions by dynamic mechanical analysis (DMA) using a novel disposable powder holder. Pharmaceutics 2:78–90.10.3390/pharmaceutics2020078Search in Google Scholar PubMed PubMed Central

Anugwom, I., Mäki-Arvela, P., Virtanen, P., Willför, S., Damlin, P., Hedenström, M., Mikkola, J.-P. (2012) Treating birch wood with a switchable 1,8-diazabicyclo-[5.4.0]-undec-7-ene-glycerol carbonate ionic liquid. Holzforschung 66:809–815.10.1515/hf-2011-0226Search in Google Scholar

Backman, A.C., Lindberg, K.A.H. (2001) Differences in wood material responses for radial and tangential direction as measured by dynamic mechanical thermal analysis. J. Mater. Sci. 36:3777–3783.Search in Google Scholar

Chowdhury, S., Frazier, C.E. (2013) Compressive-torsion DMA of yellow-poplar wood in organic media. Holzforschung 67:161–168.10.1515/hf-2011-0167Search in Google Scholar

Chowdhury, S., Fabiyi, J., Frazier, C.E. (2010) Advancing the dynamic mechanical analysis of biomass: comparison of tensile-torsion and compressive torsion DMA. Holzforschung 64:747–756.10.1515/hf.2010.123Search in Google Scholar

Clas, S.-d., Lalonde, K., Khougaz, K., Dalton, C.R., Bilbeisi, R. (2012) Detection of a minor amorphous phase in crystalline etoricoxib by dynamic mechanical analysis: comparison with Raman spectroscopy and modulated differential scanning calorimetry. J. Pharm. Sci. 101:558–565.Search in Google Scholar

Fort, D.A., Remsing, R.C., Swatloski, R.P., Moyna, P., Moyna, G., Rogers, R.D. (2007) Can ionic liquids dissolve wood? Processing and analysis of lignocellulosic materials with 1-n-butyl-3-methylimidazolium chloride. Green Chem. 9:63–69.10.1039/B607614ASearch in Google Scholar

Goring, D.A.I. (1963) Thermal softening of lignin, hemicellulose and cellulose. Pulp Pap. Mag. Can. 64:517–527.Search in Google Scholar

Guigo, N., Mija, A., Vincent, L., Sbirrazzuoli, N. (2009) Molecular mobility and relaxation process of isolated lignin studied by multifrequency calorimetric experiments. Phys. Chem. Chem. Phys. 11:1227–1236.Search in Google Scholar

Hafrén, J., Fujino, T., Itoh, T. (1999) Changes in cell wall architecture of differentiating tracheids of Pinus thunbergii during lignification. Plant Cell Physiol. 40:532–541.10.1093/oxfordjournals.pcp.a029574Search in Google Scholar

Hafrén, J., Fujino, T., Itoh, T., Westermark, U., Terashima, N. (2000) Ultrastructural changes in the compound middle lamella of Pinus thunbergii during lignification and lignin removal. Holzforschung 54:234–240.10.1515/HF.2000.040Search in Google Scholar

Hatakeyama, H., Hatakeyama, T. (2010) Thermal properties of isolated and in situ lignin. In: Lignin and Lignans: Advances in Chemistry. Eds. Heitner, C., Dimmel, D., Schmidt, J. CRC Press, New York. pp. 301–316.10.1201/EBK1574444865-c8Search in Google Scholar

Horvath, B., Peralta, P., Frazier, C., Peszlen, I.M. (2011) Thermal softening of transgenic aspen. BioResources 6:2125–2134.Search in Google Scholar

Irvine, G. (1984) The glass transitions of lignin and hemicellulose and their measurement by differential thermal analysis. Tappi J. 67:118–121.Search in Google Scholar

Janesko, B.G. (2011) Modeling interactions between lignocellulose and ionic liquids using DFT-D. Phys. Chem. Chem. Phys. 13:11393–11401.Search in Google Scholar

Jebrane, M., Harper, D., Labbé, N., Sèbe, G. (2011) Comparative determination of the grafting distribution and viscoelastic properties of wood blocks acetylated by vinyl acetate or acetic anhydride. Carbohydr. Polym. 84:1314–1320.Search in Google Scholar

Jiang, J., Lu, J., Yan, H. (2008) Dynamic viscoelastic properties of wood treated by three drying methods measured at high-temperature range. Wood Fiber. Sci. 40:72–79.Search in Google Scholar

Kalashnik, A.T., Papkov, S.P., Rudinskaya, G.V., Milkova, L.P. (1991) Liquid crystal state of cellulose. Polym. Sci. USSR 33:107–112.Search in Google Scholar

Kalichevsky, M.T., Jaroszkiewicz, E.M., Ablett, S., Blanshard, J.M.V., Lillford, P.J. (1992) The glass transition of amylopectin measured by DSC, DMTA and NMR. Carbohydr. Polym. 18:77–88.Search in Google Scholar

Kaliyan, N., Morey, R.V. (2010) Natural binders and solid bridge type binding mechanisms in briquettes and pellets made from corn stover and switchgrass. Biomass Bioenerg. 101:1082–1090.10.1016/j.biortech.2009.08.064Search in Google Scholar PubMed

Karing, V., Kozlov, P., Wan, N.-T. (1960) Investigation of the glass phase transition temperature in cellulose. Dokl. Akad. Nauk SSSR 130:356–358.Search in Google Scholar

Kelley, S.S., Rials, T.G., Glasser, W.G. (1987) Relaxation behaviour of the amorphous components of wood. J. Mater. Sci. 22:617–624.Search in Google Scholar

Kemal, E., Adesanya, K., Deb, S. (2011) Phosphate based 2-hydroxyethyl methacrylate hydrogels for biomedical applications. J. Mater. Chem. 21:2237–2245.Search in Google Scholar

Kilpeläinen, I., Xie, H., King, A., Granstrom, M., Heikkinen, S., Argyropoulos, D.S. (2007) Dissolution of wood in ionic liquids. J. Agric. Food Chem. 55:9142–9148.10.1021/jf071692eSearch in Google Scholar PubMed

Liebner, F., Patel, I., Ebner, G., Becker, E., Horix, M., Potthast, A., Rosenau, T. (2010) Thermal aging of 1-alkyl-3-methylimidazolium ionic liquids and its effect on dissolved cellulose. Holzforschung 64:161–166.10.1515/hf.2010.033Search in Google Scholar

Mahlin, D., Wood, J., Hawkins, N., Mahey, J., Royall, P.G. (2009) A novel powder sample holder for the determination of glass transition temperatures by DMA. Int. J. Pharm. 371:120–125.Search in Google Scholar

Menard, K.P. Dynamic Mechanical Analysis: A Practical Introduction. CRC Press, London, 1999.10.1201/9781420049183Search in Google Scholar

Nakamura, A., Miyafuji, H., Saka, S. (2010) Liquefaction behavior of Western red cedar and Japanese beech in the ionic liquid 1-ethyl-3-methylimidazolium chloride. Holzforschung 64:289–294.10.1515/hf.2010.042Search in Google Scholar

Obataya, E., Furuta, Y., Gril, J. (2003) Dynamic viscoelastic properties of wood acetylated with acetic anhydride solution of glucose pentaacetate. J. Wood Sci. 49:152–157.10.1007/s100860300024Search in Google Scholar

Östberg, G., Salmen, L., Terlecki, J. (1990) Softening temperature of moist wood measured by differential scanning calorimetry. Holzforschung 44:223–225.10.1515/hfsg.1990.44.3.223Search in Google Scholar

Ou, R., Xie, Y., Wolcott, M.P., Yuan, F., Wang, Q. (2014a) Effect of wood cell wall composition on the rheological properties of wood fiber/high density polyethylene composites. Compos. Sci. Technol. 93:68–75.10.1016/j.compscitech.2014.01.001Search in Google Scholar

Ou, R., Xie, Y., Wang, Q., Sui, S., Wolcott, M.P. (2014b) Effects of ionic liquid on the rheological properties of wood flour/high density polyethylene composites. Compos. Part A Appl. Sci. 61:134–140.10.1016/j.compositesa.2014.02.017Search in Google Scholar

Ou, R., Xie, Y., Wang, Q., Sui, S., Wolcott, M.P. (2014c) Thermoplastic deformation of ionic liquids plasticized poplar wood measured by a non-isothermal compression technique. Holzforschung 68:555–566.10.1515/hf-2013-0136Search in Google Scholar

Paes, S.S., Sun, S., MacNaughtan, W., Ibbett, R., Ganster, J., Foster, T.J., Mitchell, J.R. (2010) The glass transition and crystallization of ball milled cellulose. Cellulose 17:693–709.10.1007/s10570-010-9425-7Search in Google Scholar

Peng, X.-W., Ren, J.-L., Sun, R.-C. (2010) Homogeneous esterification of xylan-rich hemicelluloses with maleic anhydride in ionic liquid. Biomacromolecules 11:3519–3524.10.1021/bm1010118Search in Google Scholar PubMed

Pu, Y., Jiang, N., Ragauskas, A.J. (2007) Ionic liquid as a green solvent for lignin. J. Wood Chem. Technol. 27:23–33.Search in Google Scholar

Qu, C., Kishimoto, T., Hamada, M., Nakajima, N. (2013) Dissolution and acetylation of ball-milled lignocellulosic biomass in ionic liquids at room temperature: application to nuclear magnetic resonance analysis of cell-wall components. Holzforschung 67:25–32.10.1515/hf-2012-0037Search in Google Scholar

Remsing, R.C., Swatloski, R.P., Rogers, R.D., Moyna, G. (2006) Mechanism of cellulose dissolution in the ionic liquid 1-n-butyl-3-methylimidazolium chloride: a 13C and 35/37Cl NMR relaxation study on model systems. Chem. Commun. 1271–1273.10.1039/b600586cSearch in Google Scholar PubMed

Rong, M.Z., Zhang, M.Q., Liu, Y., Yang, G.C., Zeng, H.M. (2001) The effect of fiber treatment on the mechanical properties of unidirectional sisal-reinforced epoxy composites. Compos. Sci. Technol. 61:1437–1447.Search in Google Scholar

Royall, P.G., Huang, C.-y., Tang, S.-w. J., Duncan, J., Van-de-Velde, G., Brown, M.B. (2005) The development of DMA for the detection of amorphous content in pharmaceutical powdered materials. Int. J. Pharm. 301:181–191.Search in Google Scholar

Salmén, L. (1984) Viscoelastic properties of in situ lignin under water-saturated conditions. J. Mater. Sci. 19:3090–3096.Search in Google Scholar

Satheesh Kumar, M.N., Mohanty, A.K., Erickson, L., Misra, M. (2009) Lignin and its applications with polymers. J. Biobased. Mater. Bio. 3:1–24.Search in Google Scholar

Silalai, N., Roos, Y.H. (2011) Mechanical relaxation times as indicators of stickiness in skim milk-maltodextrin solids systems. J. Food Eng. 106:306–317.10.1016/j.jfoodeng.2011.05.018Search in Google Scholar

Soutari, N., Buanz, A.B.M., Gul, M.O., Tuleu, C., Gaisford, S. (2012) Quantifying crystallisation rates of amorphous pharmaceuticals with dynamic mechanical analysis (DMA). Int. J. Pharm. 423:335–340.Search in Google Scholar

Stelte, W., Clemons, C., Holm, J.K., Ahrenfeldt, J., Henriksen, U.B., Sanadi, A.R. (2011) Thermal transitions of the amorphous polymers in wheat straw. Ind. Crop. Prod. 34:1053–1056.Search in Google Scholar

Stelte, W., Clemons, C., Holm, J.K., Ahrenfeldt, J., Henriksen, U.B., Sanadi, A.R. (2012) Fuel pellets from wheat straw: the effect of lignin glass transition and surface waxes on pelletizing properties. BioEnerg. Res. 5:450–458.10.1007/s12155-011-9169-8Search in Google Scholar

Sugiyama, M., Norimoto, M. (1996) Temperature dependence of dynamic viscoelasticities of chemically treated woods. Mokuzai Gakkaishi 42:1049–1056.Search in Google Scholar

Sugiyama, M., Obataya, E., Norimoto, M. (1998) Viscoelastic properties of the matrix substance of chemically treated wood. J. Mater. Sci. 33:3505–3510.Search in Google Scholar

Sun, N., Das, S., Frazier, C.E. (2007) Dynamic mechanical analysis of dry wood: linear viscoelastic response region and effects of minor moisture changes. Holzforschung 61:28–33.10.1515/HF.2007.006Search in Google Scholar

Swatloski, R.P., Spear, S.K., Holbrey, J.D., Rogers, R.D. (2002) Dissolution of cellose with ionic liquids. J. Am. Chem. Soc. 124:4974–4975.Search in Google Scholar

Szcześniak, L., Rachocki, A., Tritt-Goc, J. (2008) Glass transition temperature and thermal decomposition of cellulose powder. Cellulose 15:445–451.10.1007/s10570-007-9192-2Search in Google Scholar

Takahashi, I., Sugimoto, T., Takasu, Y., Yamasaki, M., Sasaki, Y., Kikata, Y. (2010) Preparation of thermoplastic molding from steamed Japanese beech flour. Holzforschung 64: 229–234.10.1515/hf.2010.035Search in Google Scholar

Viell, J., Marquardt, W. (2011) Disintegration and dissolution kinetics of wood chips in ionic liquids. Holzforschung 65:519–525.10.1515/hf.2011.072Search in Google Scholar

Vittadini, E., Dickinson, L.C., Chinachoti, P. (2001) 1H and 2H NMR mobility in cellulose. Carbohydr. Polym. 46:49–57.Search in Google Scholar

Wang, Q., Ou, R., Shen, X., Xie, Y. (2011) Plasticizing cell walls as a strategy to produce wood-plastic composites with high wood content by extrusion processes. BioResources 6:3621–3622.Search in Google Scholar

Wolcott, M.P., Shutler, E.L. (2003) Temperature and moisture influence on compression-recovery behavior of wood. Wood Fiber. Sci. 35:540–551.Search in Google Scholar

Zhu, S., Wu, Y., Chen, Q., Yu, Z., Wang, C., Jin, S., Ding, Y., Wu, G. (2006) Dissolution of cellulose with ionic liquids and its application: a mini-review. Green Chem. 8:325–327.10.1039/b601395cSearch in Google Scholar

Received: 2014-3-16
Accepted: 2014-6-18
Published Online: 2014-7-17
Published in Print: 2015-2-1

©2015 by De Gruyter

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