Skip to content
Licensed Unlicensed Requires Authentication Published by De Gruyter July 18, 2006

The hydration of paper studied with solid-state magnetisation-exchange 1H NMR spectroscopy

Christopher J. Garvey, Ian H. Parker, George P. Simon and Andrew K. Whittaker
From the journal


The wide-line 1H nuclear magnetic resonance (NMR) spectrum of paper in equilibrium with ambient humidity consists of super-imposed relatively broad and narrow lines. The narrower line is of the order of 2 kHz wide at half the maximum height, while the broader line is of the order of 40 kHz in width at half height. On the basis of these line widths, the narrow line is assigned to water sorbed to the paper, and the broad line to the polymeric constituents of the paper. It was not possible to distinguish between the various polymeric components of paper contributing to the 1H NMR spectra. A modified Goldman-Shen pulse sequence was used to generate a spatial magnetisation gradient between the polymer and water phases. The exchange of magnetisation between protons associated with water and those associated with the macromolecules in paper was observed. The exchange of magnetisation is discussed within a heat transfer model for homonuclear dipolar coupling, with exchange being characterised by a spin-diffusion coefficient. Consideration of the magnitude of the initial rate of the exchange process and estimates of the spin-spin relaxation times based on 1H line widths indicate that some water must exist in a sufficiently immobile state as to allow homonuclear dipolar interactions between adjacent polymer and water protons. Thus, water sorbed onto paper must exist in at least two states in mass exchange with each other. This observation allows certain conclusions to be drawn about the ratio of free/bound water as a function of moisture content and the dispersal of water within the polymer matrix.


Corresponding author. Current address: Australian Nuclear Science and Technology Organisation, PMB 1, Menai, NSW 2234 Australia


Abragam, A. The Principles of Nuclear Magnetism. Oxford University Press, Oxford, 1961.10.1063/1.3057238Search in Google Scholar

Abragam, A., Goldman, M. Nuclear Magnetism: Order and Disorder. Clarendon Press, Oxford, 1982.10.1063/1.2914893Search in Google Scholar

Auñón, J.I., Chandrasekar, V. Introduction to Probability and Random Processes. McGraw Hill, New York, 1997.Search in Google Scholar

Bloembergen, N. (1949) On the interaction of nuclear spins in a crystalline lattice. Physica15:387–426.10.1016/0031-8914(49)90114-7Search in Google Scholar

Brownstein, K.R., Tarr, C.E. (1979) Importance of classical diffusion in NMR studies of water in biological cells. Phys. Rev.19:2446–2453.10.1103/PhysRevA.19.2446Search in Google Scholar

Callaghan, P.T. Principles of Nuclear Magnetic Resonance Microscopy. Oxford University Press, Oxford, 1993.Search in Google Scholar

Capitani, D., Segre, A.L., Attanasio, D., Blicharska, B., Focher, B., Capretti, G. (1996) 1H NMR relaxation study of paper as a system of cellulose and water. Tappi J.79(6):113–122.Search in Google Scholar

Caravatti, P., Neuenschwander, P., Ernst, R.R. (1985) Characterization of heterogeneous polymer blends by two-dimensional proton spin diffusion spectroscopy. Macromolecules18:119–122.10.1021/ma00143a020Search in Google Scholar

Clauss, J., Schmidt-Rohr, K., Spiess, H.W. (1998) Determination of domain sizes in heterogeneous polymers by solid-state NMR. Acta Polym.44:1–17.Search in Google Scholar

Cory, D.G., Garroway, A.N. (1990) Measurement of translational displacement probabilities by NMR: an indicator of compartmentation. Magn. Reson. Med.14:435–444.10.1002/mrm.1910140303Search in Google Scholar

Crank, J. The Mathematics of Diffusion. Clarendon Press, Oxford, 1975.Search in Google Scholar

Czihak, C., Muller, M., Schober, H., Heux, L., Vogl, G. (1999) Dynamics of water adsorbed to cellulose. Physica B266:87–91.10.1016/S0921-4526(98)01497-5Search in Google Scholar

Deodhar, S., Luner, P. (1980) Measurement of bound (nonfreezing) water by differential scanning calorimetry. In: Water in Polymers. Ed. Rowland, S.P. American Chemical Society, Washington, DC. pp. 273–286.10.1021/bk-1980-0127.ch016Search in Google Scholar

Fatkullin, N.F., Yatsenko, G.A., Kimmich, R., Fisher, E. (1998) Theory of spin diffusion in liquid-phase polymer systems. J. Exp. Theor. Phys.87:294–302.10.1134/1.558659Search in Google Scholar

Filbotte, S.G., Menon, R.S., Mackaym A.L., Hailey, J.R.T. (1990) Proton magnetic resonance of Western red cedar. Wood Fiber Sci.22:362–378.Search in Google Scholar

Fisher, E., Kimmich, R., Fatkullin, N.F. (1997) Spin diffusion in melts of entangled polymers. J. Chem. Phys.106:9883–9888.10.1063/1.473876Search in Google Scholar

Friebel, S., Harris, R.K., Kenwright, A.M. (1997) Computer simulations of the Goldman-Shen experiment: evaluation of techniques for minimizing the influence of spin-lattice relaxation. Magn. Reson. Chem.35:290–296.10.1002/(SICI)1097-458X(199705)35:5<290::AID-OMR85>3.0.CO;2-ZSearch in Google Scholar

Froix, M.F., Nelson, R. (1975) The interaction of water with cellulose from nuclear magnetic resonance relaxation times. Macromolecules8:726–730.10.1021/ma60048a011Search in Google Scholar

Fukushima, E., Roeder, S.B.W. Experimental Pulse NMR: A Nuts and Bolts Approach. Addison-Wesley, Reading, 1981.Search in Google Scholar

Garvey, C.J., Simon, G.P., Knott, R.B., Whittaker, A.K., Parker, I.H. (2001) An experimental study by NMR and SANS of the hydration of paper sheets. In: Proceedings of the 12th Fundamental Symposium of Papermaking, University of Oxford, Vol. 1, 359–380.Search in Google Scholar

Garvey, C.J., Parker, I.H., Knott, R.B., Simon, G.P. (2004) Smallangle scattering in the Porod region from hydrated paper sheets at varying humidities. Holzforschung58:473–479.10.1515/HF.2004.071Search in Google Scholar

Goldman, M., Shen, L. (1966) Spin-spin relaxation in LaF3. Phys. Rev.144:321–331.10.1103/PhysRev.144.321Search in Google Scholar

Hill, T.L. An Introduction to Statistical Thermodynamics. Dover, New York, 1986.Search in Google Scholar

Jandel Scientific Software, Peakfit, V4, 1995.Search in Google Scholar

Kenwright, A.M., Packer, K.J. (1990) On T1 cancellation schemes in Goldman-Shen-type experiments. Chem. Phys. Lett.173:471–475.10.1016/0009-2614(90)87237-LSearch in Google Scholar

Kulik, A.S., de Costa, J.R., Haverkamp, J. (1994) Water organization and molecular mobility in maize starch investigated by two-dimensional solid-state NMR. J. Agric. Food Chem.42:2803–2807.10.1021/jf00048a028Search in Google Scholar

Landfester, K., Spiess, H.W. (1998) Characterization of interphases in core-shell latexes by solid-state NMR. Acta Polym.49:451–464.10.1002/(SICI)1521-4044(199809)49:9<451::AID-APOL451>3.0.CO;2-USearch in Google Scholar

McBrierty, V.J., Packer, K.J. Nuclear Magnetic Resonance in Solid Polymers. Cambridge University Press, Cambridge, 1993.10.1017/CBO9780511525278Search in Google Scholar

McBrierty, V.J., Keely, C.M., Coyle, F.M., Xu, H., Vij, J.K. (1996) Hydration and plasticization effects in cellulose acetate: molecular motion and relaxation. Faraday Discuss.103:255–268.10.1039/fd9960300255Search in Google Scholar

McBrierty, V.J., Martin, S.J., Karasz, F.E. (1999) Understanding hydrated polymers: the perspective of NMR. J. Mol. Liquids80:179–205.10.1016/S0167-7322(99)80007-5Search in Google Scholar

Mellinger, F., Wilhelm, M., Landfester, K., Spiess, H.W., Haunschild, A., Packusch, J. (1998) Structure of water-containing latexes: remagnetization effects during solid-state NMR spin-diffusion experiments. Acta Polym.49:108–115.10.1002/(SICI)1521-4044(199802)49:2/3<108::AID-APOL108>3.0.CO;2-PSearch in Google Scholar

Mellinger, F., Wilhelm, M., Spiess, H.W. (1999) Calibration of 1H NMR spin diffusion coefficients for mobile polymers through transverse relaxation measurements. Macromolecules32:4686–4691.10.1021/ma9820265Search in Google Scholar

Nissan, A.H. (1976) H-Bond dissociation in hydrogen bond-dominated solids. Macromolecules9:840–850.10.1021/ma60053a026Search in Google Scholar

Packer, K.J., Pope, J.M., Yeung, R.R. (1984). The effects of morphology on 1H NMR spectra and relaxation in semicrystalline polyolefins. J. Polym. Sci. Phys. Ed.22:589–616.Search in Google Scholar

Powles, J.G., Mansfield, P. (1962) Double-pulse nuclear-resonance transients in solids. Phys. Lett.2:58–59.10.1016/0031-9163(62)90147-6Search in Google Scholar

Powles, J.G., Strange, J.H. (1963) Zero time resolution nuclear magnetic resonance transients in solids. Proc. Phys. Soc.82:6–15.10.1088/0370-1328/82/1/303Search in Google Scholar

Radloff, D., Boeffel, C., Spiess, H.W. (1996) Cellulose and cellulose/poly(vinyl alcohol) blends. 2. Water organization revealed by solid-state NMR spectroscopy. Macromolecules29:1528–1534.Search in Google Scholar

Resing, H.A. (1965) Apparent phase-transition effect in the NMR spin-spin relaxation time caused by a distribution of correlation times. J. Chem. Phys.43:669–678.10.1063/1.1696791Search in Google Scholar

Resing, H.A. (1972) NMR relaxation of adsorbed molecules with emphasis on adsorbed water. Adv. Mol. Relaxation Processes3:199–226.10.1016/0001-8716(72)80034-8Search in Google Scholar

Salmén, N.L., Back, E.L. (1977) The influence of water on the glass transition temperature of cellulose. Tappi J.60:137–140.Search in Google Scholar

Salmén, N.L., Back, E.L. (1980) Moisture-dependant thermal softening of paper evaluated by its elastic modulus. Tappi J.63:117–121.Search in Google Scholar

Schmidt-Rohr, K., Spiess, H.W. Multidimensional Solid State NMR and Polymers. Academic Press, San Diego 1994.Search in Google Scholar

Spiegel, S., Schmidt-Rohr, K., Boeffel, C., Spiess, H.W. (1993) 1H spin diffusion coefficients of highly mobile polymers. Polymer Commun.34:4566–4569.10.1016/0032-3861(93)90166-8Search in Google Scholar

Spiegel, S., Schmidt-Rohr, K., Boeffel, C., Spiess, H.W. (1994) 1H spin diffusion coefficients of highly mobile polymers. Polymer34:4566–4569.Search in Google Scholar

Standards Australia (2001) AS/NZS 1301.209s, Methods of test for pulp and paper (metric units) – Laboratory processing of pulp – PFI mill method.Search in Google Scholar

Starkweather, H.W. (1975) Some aspects of water clusters in polymers. Macromolecules8:476–479.10.1021/ma60046a020Search in Google Scholar

VanderHart, D.L., McFadden, G.B. (1996) Some perspectives on the interpretation of proton NMR spin diffusion data in terms of polymer morphologies. Solid State NMR7:45–66.10.1016/0926-2040(96)01233-7Search in Google Scholar

Venkateswaran, A. (1970) Sorption of aqueous and nonaqueous media by wood and cellulose. Chem. Rev.70:619–637.10.1021/cr60268a001Search in Google Scholar

Wang, J. (1996) On the determination of domain sizes in polymers by spin diffusion. J. Chem. Phys.104:4850–4858.10.1063/1.471179Search in Google Scholar

Wilson, C.W., Pake, G.E. (1953) Nuclear magnetic resonance determination of degree of crystallinity in two polymers. J. Polym. Sci.10:503–505.10.1002/pol.1953.120100508Search in Google Scholar

Zimm, B.H., Lundberg, J.L. (1956) Sorption of vapors by high polymers. J. Phys. Chem.60:425–428.10.1021/j150538a010Search in Google Scholar

Published Online: 2006-07-18
Published in Print: 2006-07-01

©2006 by Walter de Gruyter Berlin New York