Abstract
The microscopic changes in the structure of paper at different equilibrium moisture contents were examined using the novel technique of contrast variation small angle neutron scattering (SANS). Contrast variation, by appropriate selection of the H2O:D2O ratio, was used to simplify the scattering from hydrated paper to a two-phase approximation. The two phases were paper polymers (cellulose, lignin and hemicelluloses) and a phase consisting of water and voids. The two-phase approximation is justified by consideration of the chemistry and density of each of the polymer species belonging to paper, and by matching the scattering length density of the sorbed moisture to air. The neutron intensity at the higher scattering angles examined was successfully fitted using the Porod law, which is applicable to scattering from a two-phase system at the high scattering angle limit. This limit is related to the specific surface area between the two phases. The limiting scattered intensity of neutrons was found to increase with increasing moisture content for a range of paper materials. It is concluded that the sorption of water increased the limiting intensity because water disrupted polymer-polymer bonding. The Porod law also predicts the slope of the intensity/scattering angle curve at the high scattering angle limit.
References
Adamson, A.W. (1990) Physical Chemistry of Surfaces. Wiley-Interscience, New York. pp. 647–648.Search in Google Scholar
Beaucage, G. (1995) Approximations leading to a unified exponential/power-law approach to small angle scattering. J. Appl. Cryst.28:717–728.10.1107/S0021889895005292Search in Google Scholar
Brunauer, S., Copeland, L.E., Kantro, D.L. (1966) The Langmuir and BET Theories. In: The Solid-Gas Interface, Vol. 1. Ed. Flood, E.A. Marcel Dekker, New York. pp. 77–104.Search in Google Scholar
Cranshaw, J., Vickers, M.E., Briggs, N.P., Heenan, R.K., Cameron, R.E. (2000) The hydration of TENCEL® cellulose fibres studied using contrast variation in small angle neutron scattering. Polymer41:1873–1881.10.1016/S0032-3861(99)00331-6Search in Google Scholar
CRC Handbook of Chemistry and Physics. CRC Press, Cleveland, 2000. pp. 15–25.Search in Google Scholar
Feigin, L.A., Svergun, D.I. - Structure Analysis by Small Angle X-ray and Neutron Scattering. Plenum Press, New York, 1969. pp. 107–14.Search in Google Scholar
Fisher, E.W., Herchenroder, P., Manley, R.S.J., Stamm, M. (1976) Small-angle scattering of selectively deuterated cellulose. Macromolecules11:213–217.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, pp. 359–380.Search in Google Scholar
Greenland, D.J., Quirk, J.P. (1964) Determination of the total specific surface areas of soils by adsorption of cetyl pyridinium bromide. J. Soil Sci.15:178–191.10.1111/j.1365-2389.1964.tb02217.xSearch in Google Scholar
Guinier, A., Fournet, G. - Small-Angle Scattering of X-rays. John Wiley and Sons, New York, 1955.Search in Google Scholar
Hammouda, B., Krueger, S., Glinka, C.J. (1993) Small angle neutron scattering at National Institute for Standards and Technology. J. Res. Inst. Stand. Technol.98:31–46.10.6028/jres.098.003Search in Google Scholar
Hermans, P.H., Heikens, D., Weidinger, A. (1959) A quantitative investigation on the X-ray small angle scattering of cellulose fibres. Part II The scattering power of various cellulose fibres. J. Polymer Sci.35:145–165.Search in Google Scholar
Higgins, J.S., Benoît, H.C. - Polymers and Neutron Scattering. Clarendon Press, Oxford, 1994.Search in Google Scholar
Hill, T.L. - An Introduction to Statistical Thermodynamics. Dover, New York, 1986. pp. 134.Search in Google Scholar
Howsman, J.A., Sisson, W.A. (1954) In: Cellulose and Cellulose Derivatives. Eds Ott, E., Spurlin, H.M., Graffin., M.V. Vol. 1, 2nd Edition, Interscience, New York. pp. 231–316.Search in Google Scholar
Jakob, H.F., Tschegg, S.E., Fratzl, P. (1986) Hydration Dependence of the Wood-Cell Wall Structure in Picea abies. A Small-Angle X-ray Scattering Study. Macromolecules29:8435–8440.Search in Google Scholar
Klenkova, N.I., Ivashkin, G.P. (1963) Internal surface area and capillary structure of native and mercerized cellulose. J. Appl. Chem. USSR36:398–408.Search in Google Scholar
Koberstein, J.T., Morra, B., Stein, R.S. (1980) The determination of diffuse-boundary thicknesses of polymers by small-angle X-ray scattering. J. Appl. Cryst.13:34–45.10.1107/S0021889880011478Search in Google Scholar
Krässig, H.A. - Cellulose: structure, accessibility, and reactivity. Gordon and Breach, Yverdon, 1992.Search in Google Scholar
Kratky, O., Miholic, G. (1963) Small-angle investigations with absolute intensity measurments on regenerated, air-swollen cellulose. J. Polym. Sci.Part C2:449–476.Search in Google Scholar
Li, J-C., Benham, M.J., Howe, L.D., Ross, D.K. (1989) Neutron and X-ray scattering: complementary techniques. Inst. Phys. Conf. Ser.101:155–168.Search in Google Scholar
Luzzati, V., Witz, J., Nicolaieff, A. (1961) Determination of mass and dimensions of proteins in solution by x-ray scattering measured on an absolute scale. J. Molec. Biol.3:367–378.10.1016/S0022-2836(61)80050-8Search in Google Scholar
Manley, R.S.J. (1963) Hydrolysis of cellulose triacetate crystals. J. Polymer Sci.Part A1:1893–1899.10.1002/pol.1963.100010604Search in Google Scholar
Mitropoulos, A.C., Kanellpoulos, N.K., Stefanpoulos, K.L., Heenan, R.K. (1998) Scattering by Curved and Fractal Surfaces. J. Colloid Interface Sci.203:229–230.10.1006/jcis.1998.5550Search in Google Scholar
Müller, M., Czihak, C., Schober, H., Nishiyama, Y., Vogl, G. (2000) All disordered regions of native cellulose show common low-frequency dynamics. Macromolecules33:1834–1840.10.1021/ma991227lSearch in Google Scholar
National Institute of Standards and Technology Center for Neutron Research. - NCNR SANS Data Acquisition Manual, US Department of Commerce, Gaithersburg, 1999.Search in Google Scholar
Nissan, A.H. (1976) H-bond dissociation in hydrogen bond dominated solids. Macromolecules9:840–850.10.1021/ma60053a026Search in Google Scholar
Perrin, P., Prud’homme, R.E. (1994) SAXS measurements of interfacial thickness in amorphous polymer blends containing a diblock copolymer. Macromolecules27:1852–1860.10.1021/ma00085a029Search in Google Scholar
Porod, G. (1951) The x-ray small angle scattering of close packed colloid systems. I. Kolloid-Z.124:83–114.10.1007/BF01512792Search in Google Scholar
Porod, G. (1952) The x-ray small angle scattering of close packed colloid systems. II. Kolloid-Z.125:108–122.10.1007/BF01526289Search in Google Scholar
Roberts, G.A.F. (1996) In: Paper Chemistry. Ed. Roberts, J.C. Blackie Academic, Glasgow.Search in Google Scholar
Salmén, N.L., Back, E.L. (1977) The influence of water on the glass transition temperature of cellulose. Tappi J.60(12):137–140.Search in Google Scholar
Salmén, N.L., Back, E.L. (1980) Moisture-dependant thermal softening of paper evaulated by its elastic modulus. Tappi J.63(6):117–121.Search in Google Scholar
Schwartz, M. - Principles of Electrodynamics. Dover, New York, 1987. pp. 223–224.Search in Google Scholar
Sears, V.F. (1992) Neutron scattering length and cross sections. Neutron News3:26–37.10.1080/10448639208218770Search 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
Statton, W.O. (1956) Crystallite regularity and void content in cellulose fibres as shown by small angle X-ray scattering. J. Polymer Sci.22:385–397.10.1002/pol.1956.1202210204Search in Google Scholar
van de Hulst, H.C. - Light Scattering by Small Particles. Dover, New York, 1986. pp. 3.Search in Google Scholar
© Walter de Gruyter