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Determination of crystallinity index of cellulose depending on sample preparation and analysis instruments

시료 조건 및 측정방법에 따른 셀룰로오스의 결정화도 평가

  • 안정언 (서울대학교 농업생명과학대학 산림과학부) ;
  • 윤혜정 (서울대학교 농업생명과학대학 산림과학부) ;
  • 정양진 (한국조폐공사) ;
  • 김태영 (한국조폐공사)
  • Received : 2012.07.25
  • Accepted : 2012.08.09
  • Published : 2012.08.30

Abstract

The crystallinity index is an important characteristic of cellulose. The crystallinity value is different depending on the adopted instrument. In this study, we determined a crystallinity index of cotton and wood celluloses using wide-angle X-ray scattering (WAXS), powder X-ray diffractometer (PXRD), and cross polarization/magic angle spinning solid-state $^{13}C$ nuclear magnetic resonance spectroscopy (CP/MAS solid-state $^{13}C$ NMR). The specimen was prepared in forms of powder, sheet and pallet. With the comparison of the obtained crystallinity indices of the cellulose, the effects of the analysis instrument, the sample preparation and analysis method were investigated. Among three instruments, the crystallinity indices by PXRD and NMR had a good relationship and reproducibility, and WAXS gave the crystallinity index with poor reproducibility. In the case of analysis methods of crystallinity indices, the Segal method showed higher value than that of the Ruland-Vonk method. We expect that this study would be applicable to evaluate the crystallinity index of various cellulose materials with accuracy and reproducibility.

Keywords

References

  1. Freytag, R., and Donze, J., -J., Handbook of fibre science and technology, Vol. 1, Chemical precessing of fibres and fabrics - Fundamentals and preparation, Part A., Marcell Dekker Inc., New York, (1983).
  2. Zhao, H., Kwak, J. H., Wang, Y., Franz, J. A., White, J. M., and Holladay, J. E., Effects of crystallinity on dilute acid hydrolysis of cellulose by cellulose ball-milling study, Energy & Fuels, 20: 807-811 (2006). https://doi.org/10.1021/ef050319a
  3. Teeaar, R., Serimma, R., and Paakkari, T., Crystallinity of cellulose, as determined by CP/MAS NMR and XRD methods, Polym Bull 17, 231-237 (1987).
  4. Evans, R., Newman, R. H., Roick, U. C., Sucking, I. D., and Wallis, A. F. A., Changes in cellulose crystallinity during kraft pulping. comparison of infrared , X-ray diffraction and solid state NMR resault, Holzforschung 49: 498-504 (1995). https://doi.org/10.1515/hfsg.1995.49.6.498
  5. Park, S., Johnson, D. K., Ishizawa, C. I., Parilla P. A., and Davis M. F., Measuring the crystallinity index of cellulose by solid state $^{13}C$ nuclear magnetic resonance, Cellulose, 16:641-647 (2009). https://doi.org/10.1007/s10570-009-9321-1
  6. Thygesen, A., Oddershede, J., Lilholt, H., Thomsen, A., and Stahl, K., On the determination of crystallinity and cellulose content in plant fibres, Cellulose, 12:563-576 (2005). https://doi.org/10.1007/s10570-005-9001-8
  7. Segal L., Creely, J. J., Martin A. E., and Conrad C. M., An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Textile Res. J., 29: 786-794 (1959). https://doi.org/10.1177/004051755902901003
  8. Schroeder, L. R., Gentile, V. M., and Atalla, R. H., Nonndegrative preparation of amorphous cellulose, J Wood Chem Technol, 6: 1-14 (1986). https://doi.org/10.1080/02773818608085213
  9. Husson, E., Buchoux, S., Avondo, C., Cailleu, D., Djellab, K., Gosselin, I., Wattraint, O., and Sarazin, Catherine., Enzymatic hydrolysis of ionic liquid-pretreated celluloses: Contribution of $CP-MAS^{13}C$ NMR and SEM, Bioresource Technology, 102: 7335-7342 (2011). https://doi.org/10.1016/j.biortech.2011.04.097
  10. Mwaikambo, L. Y., and Ansell, M. P., The effect of chemical treatment on the properties of hemp, sisal, jute and kapok for composite reinforcement, Chem, 272:108-116 (1999).
  11. Maunu, S., Liitia, T., Kauliomaki, S., Hortling, B., and Sundquist, J., 13C CPMAS NMR investigations of cellulose polymorphs in different pulps, Cellulose, 7:147-159 (2000). https://doi.org/10.1023/A:1009200609482
  12. Isogai, A., Cellulosic polymers, blends and composites, Gilbert, R. D. (ed.), Hanser Gardner Publications, Inc., pp. 1-24 (1994).
  13. Wakelin, J. H., Virgin, H. S., and Crystal, E., Development and comparison of two X-ray methods for determining the crystallinity of cotton cellulose, J. App Phys, 30(11): 1654-1662 (1959). https://doi.org/10.1063/1.1735031
  14. Hatakeyama, T., Structure and properties of the amorphous region of cellulose, Kennedy, J.F. et al (ed.), Ellis Horwood Ltd., pp. 45-52 (1989).
  15. Lahaye, M., Rondeau-Mouro, C., Deniaud, E., and Buleon, A., Solid-state $^{13}C$ NMR spectroscopy studies of xylans in the cell wall of Palmaria palmata, Carbohydrate Research 338, 1559-1569 (2003). https://doi.org/10.1016/S0008-6215(03)00241-6