, Volume 17, Issue 3, pp 539–545 | Cite as

Molecular orientation in the Nematic Ordered Cellulose film using polarized FTIR accompanied with a vapor-phase deuteration method



Previously, the authors reported “Nematic Ordered Cellulose (NOC)” that is a well-ordered state of β-1,4-glucan chains without exhibiting typical X-ray diffraction patterns of any cellulose polymorphs (Togawa and Kondo 1999; Kondo et al. 2001; Kondo 2007). The NOC was prepared by stretching water-swollen gel-like films at the draw ratio of 2.0 to provide highly oriented β-1,4-glucan molecular chains of cellulose, which was proved by the high resolution TEM observation. In this paper, a detailed study of the unique ordered state of the NOC was attempted to characterize orientation of the main chains as well as the OH groups of molecules using polarized FTIR accompanied with a vapor-phase deuteration method. The dichroic analysis suggested that the main chains were fairly oriented in the stretching direction whereas the OH groups remained unoriented. The disordered state of the OH groups regardless of the oriented state for the main chain may hinder the oriented crystallization during the preparation of NOC films.


Nematic ordered cellulose Orientation Polarized FTIR Dichroism Deuteration 


  1. Dikshit AK, Kaito A (2003) Crystallization and orientation behaviors in isotactic polystyrene and poly(2, 6-dimethylphenylene oxide) blends. Polymer 44:6647–6656CrossRefGoogle Scholar
  2. Dulmage WJ, Geddes AL (1958) Structure of drawn polyethylene terephthalate. J Polym Sci 31:499–512CrossRefGoogle Scholar
  3. Gustafsson G, Inganäs O, Österholm H, Laakso J (1991) X-ray diffraction and infra-red spectroscopy studies of oriented poly(3-alkylthiophenes). Polymer 32:1574–1580CrossRefGoogle Scholar
  4. Hishikawa Y, Togawa E, Kataoka Y, Kondo T (1999) Characterization of amorphous domains in cellulosic materials using a FTIR deuteration monitoring analysis. Polymer 40:7117–7124CrossRefGoogle Scholar
  5. Hishikawa Y, Inoue S-I, Magoshi J, Kondo T (2005) Novel tool for characterization of noncrystalline regions in cellulose: a FTIR deuteration monitoring and generalized two-dimensional correlation spectroscopy. Biomacromolecules 6:2468–2473CrossRefGoogle Scholar
  6. Kaito A, Yatabe T, Ohnishi S, Tanigaki N, Yase K (1999) Orientation behavior in a comblike polysilane having long alkyl side chains. Macromolecules 32:5647–5654CrossRefGoogle Scholar
  7. Kandilioti G, Govaris GK, Gregoriou VG (2004) Vibrational spectroscopic study on the origin of stress oscillation during step-wise stretching in poly(ethylene terephthalate). Appl Spectrosc 58:1082–1092CrossRefGoogle Scholar
  8. Karacan I (2006) Molecular structure and orientation of gel-spun polyethylene fibers. J Appl Polym Sci 101:1317–1333CrossRefGoogle Scholar
  9. Koenig JL, Cornell SW, Witenhafer DE (1967) Infrared technique for the measurement of structural changes during the orientation process in polymers. J Polym Sci Part A 2(5):301–313Google Scholar
  10. Kondo T (2007) Nematic ordered cellulose: its structure and properties. In: Brown RM Jr, Saxena IM (eds) Cellulose: molecular and structural biology selected articles on the synthesis, structure, and applications of cellulose, 1st edn. Springer, New York, pp 285–305Google Scholar
  11. Kondo T, Kataoka Y, Hishikawa Y (1998) Novel approaches using FTIR spectroscopy to study the structure of crystalline and noncrystalline cellulose. In: Heinze TJ, Glasser WG (eds) Cellulose derivatives, 1st edn. ACS Symposium Series 688 American Chemical Society, Washington, DC, pp 173–183Google Scholar
  12. Kondo T, Brown RM Jr, Togawa E (2001) “Nematic ordered cellulose”: a concept of glucan chain association. Biomacromolecules 2:1324–1330CrossRefGoogle Scholar
  13. Kondo T, Nojiri M, Hishikawa Y, Togawa E, Romanovicz D, Brown RM Jr (2002) Biodirected epitaxial nanodeposition of polymers on oriented macromolecular templates. Proc Natl Acad Sci USA 99:14008–14013CrossRefGoogle Scholar
  14. Lee HS, Park SC, Kim YH (2000) Structural changes of poly(trimethylene terephthalate) film upon uniaxial and biaxial drawing. Macromolecules 33:7994–8001CrossRefGoogle Scholar
  15. Liang CY, Krimm S (1957) Orientation in polyethylene terephthalate film. J Chem Phys 27:327–328CrossRefGoogle Scholar
  16. Liang CY, Marchessault RH (1959a) Infrared spectra of crystalline polysaccharides I. Hydrogen bonds in native cellulose. J Polym Sci 37:385–395CrossRefGoogle Scholar
  17. Liang CY, Marchessault RH (1959b) Infrared spectra of crystalline polysaccharides. II. Native cellulose in the region from 640 to 1700 cm−1. J Polym Sci 39:269–278CrossRefGoogle Scholar
  18. Liang CY, Marchessault RH (1960) Infrared spectra of crystalline polysaccharides. IV. The use of inclined incidence in the study of oriented films. J Polym Sci 43:85–100CrossRefGoogle Scholar
  19. Lofgren EA, Jabarin SA (1994) Polarized internal reflectance spectroscopic studies of oriented poly(ethylene terephthalate). J Appl Polym Sci 51:1251–1267CrossRefGoogle Scholar
  20. Mandelkern L (2002) Crystallization of polymers, vol 1, 2nd edn. Cambridge University Press, CambridgeGoogle Scholar
  21. Mann J, Marrinan HJ (1958) Crystalline modifications of cellulose. Part II. A study with plane-polarized infrared radiation. J Polym Sci 32:357–370CrossRefGoogle Scholar
  22. Marchessault RH, Liang CY (1960) Infrared spectra of crystalline polysaccharides. III. Mercerized cellulose. J Polym Sci 43:71–84CrossRefGoogle Scholar
  23. Maréchal Y, Chanzy H (2000) The hydrogen bond network in I β cellulose as observed by infrared spectroscopy. J Mol Struct 523:183–196CrossRefGoogle Scholar
  24. Onogi S, Asada T (1967) Rheo-optical studies of high polymers. IX. A study of deformation process of low-density polyethylene by simultaneous measurements of stress, strain, and infrared absorption. J Polym Sci Part C 16:1445–1455Google Scholar
  25. Park JW, Tanaka T, Doi Y, Iwata T (2005) Uniaxial drawing of poly[(R)-3-hydroxybutyrate]/cellulose acetate butyrate blends and their orientation behavior. Macromol Biosci 5:840–852CrossRefGoogle Scholar
  26. Radhakrishnan J, Kaito A (2001) Structure formation during the isothermal crystallization of oriented amorphous poly(ethylene terephthalate) films. Polymer 42:3859–3866CrossRefGoogle Scholar
  27. Read BE, Stein RS (1968) Polarized infrared studies of amorphous orientation in polyethylene and some ethylene copolymers. Macromolecules 1:116–126CrossRefGoogle Scholar
  28. Samuels RJ (1965) Morphology of deformed polypropylene quantitative relations by combined X-ray, optical, and sonic methods. J Polym Sci Part A 3:1741–1763Google Scholar
  29. Shigematsu Y, Takada A, Nemoto N, Nitta K-H (2001) An instrument for simultaneous kinetic measurement of microscopic infrared dichroism and stress of inhomogeneous polymer thin films at constant elongation rate. Rev Sci Instrum 72:3927–3932CrossRefGoogle Scholar
  30. Sibilia JP (1971) Orientation in nylon 6 films as determined by the three-dimensional polarized infrared technique. J Polym Sci Part A2 9:27–42CrossRefGoogle Scholar
  31. Siesler VH, Krässig H, Grass F, Kratzl K, Derkosch J (1975) Strukturuntersuchungen an Cellulosefasern verschiedenen Verstrekungsgrades mittels IR-Reflexionsspektroskopie und Deuteriumaustausch. Angew Makromol Chem 42:139–165CrossRefGoogle Scholar
  32. Smith JK, Kitchen WJ, Mutton DB (1963) Structural study of cellulosic fibers. J Polym Sci Part C 2:499–513Google Scholar
  33. Stein RS, Norris FH (1956) The X-ray diffraction, birefringence, and infrared dichroism of stretched polyethylene. J Polym Sci 21:381–396CrossRefGoogle Scholar
  34. Šturcová A, His I, Wess TJ, Cameron G, Jarvis MC (2003) Polarized vibrational spectroscopy of fiber polymers: hydrogen bonding in cellulose II. Biomacromolecules 4:1589–1595CrossRefGoogle Scholar
  35. Togawa E, Kondo T (1999) Change of morphological properties in drawing water-swollen cellulose films prepared from organic solutions. A view of molecular orientation in the drawing process. J Polym Sci Part B Polym Phys 37:451–459CrossRefGoogle Scholar
  36. Tsuboi M (1957) Infrared spectrum and crystal structure of cellulose. J Polym Sci 25:159–171CrossRefGoogle Scholar
  37. Vasanthan N (2005) Determination of molecular orientation of uniaxially stretched polyamide fibers by polarized infrared spectroscopy: comparison of X-ray diffraction and birefringence methods. Appl Spectrosc 59:897–903CrossRefGoogle Scholar
  38. Voice AM, Bower DI, Ward IM (1993) Molecular orientation in uniaxially drawn poly(aryl ether ether ketones): 2. Infra-red spectroscopy study. Polymer 34:1164–1173CrossRefGoogle Scholar
  39. Voyiatzis GA, Andrikopoulos KS, Papatheodorou GN, Kamitsos EI, Chryssikos GD, Kapoutsis JA, Anastasiadis SH, Fytas G (2000) Polarized resonance raman and FTIR reflectance spectroscopic investigation of the molecular orientation in industrial poly(vinyl chloride). Macromolecules 33:5613–5623CrossRefGoogle Scholar
  40. Zbinden R (1964) Infrared spectroscopy of high polymers. Academic Press, New YorkGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2010

Authors and Affiliations

  1. 1.Forestry and Forest Products Research Institute (FFPRI)TsukubaJapan
  2. 2.Graduate School of Bioresource and Bioenvironmental Sciences & Bio-Architecture Center (KBAC)Kyushu UniversityFukuokaJapan

Personalised recommendations