, Volume 21, Issue 5, pp 3243–3255 | Cite as

Physical structure and thermal behavior of ethylcellulose

  • M. Davidovich-Pinhas
  • S. Barbut
  • A. G. Marangoni
Original Paper


The physical structure and properties of ethylcellulose (EC) powders of different molecular weights were examined. A molecular weight in the range of 20–144 kDa with a large polydispersity was determined. EC thermal analysis revealed a glass transition at ~130 °C and a melting temperature at ~180 °C. Glass transition temperatures increased with polymer molecular weight. Wide angle (WAXS) analysis detected an amorphous broad peak at q = 1.5 Å−1 and a distinct Bragg’s peak at 12.6 Å, which seems to be related to a supramolecular ordered structure of the polymer. These observations were confirmed using high temperature powder X-ray diffraction analysis where the crystalline peak disappeared above the melting temperature of the polymer. Ultra-small angle (USAXS) results were fitted to the Bouacage fractal unified model and fractals with an average size of 100–600 nm with a relatively smooth surface were predicted. This prediction was confirmed by transmission electron microscopy (TEM) images. According to our results, the EC polymer has a semi-crystalline structure, with crystalline domains within an amorphous background.


Ethyl cellulose Semi-crystalline Powder Fractal X-ray scattering 



Research supported by the Ontario Ministry of Agriculture and Food (OMAF) and the Natural Sciences and Engineering Research Council of Canada (NSERC). We acknowledge the technical assistance of Fernanda Peyronel for setting up experiments and data analysis. The author wish to thank Dr. Jan Ilavsky from the APS sector 15ID-D USAXS/SAXS facility for his help conducting both SAXS and USAXS experiments. ChemMatCARS Sector 15 is principally supported by the National Science Foundation/Department of Energy under grant number NSF/CHE-0822838. Use of the Advanced Photon Source was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.


  1. Agarwal V, Huber GW, Conner WC Jr, Auerbach SM (2011) Simulating infrared spectra and hydrogen bonding in cellulose Iβ at elevated temperatures. J Chem Phys 135:1–13CrossRefGoogle Scholar
  2. Aiache JM, Gauthier P, Aiache S (1992) New gelification method for vegetable oils I: cosmetic application. Int J Cosmetic Sci 14:228–234CrossRefGoogle Scholar
  3. Atalla RH, Isogai A (1998) Recent developments in spectroscopic and chemical characterization of cellulose. In: Dumitriu S (ed) Polysaccharides: structural diversity and functional versatility, 2nd edn. Marcel Dekker, New York, pp 123–157Google Scholar
  4. Beaucage G (1995) Approximations leading to a unified exponential/power-law approach to small-angle scattering. J Appl Cryst 28:717–728CrossRefGoogle Scholar
  5. Beaucage G (1996) Small-angle scattering from polymeric mass fractals of arbitrary mass-fractal dimension. J Appl Cryst 29:134–146CrossRefGoogle Scholar
  6. Cavalcanti OA, Petenuc B, Bedin AC, Pineda EAG, Hechenleitner AAW (2004) Characterisation of ethylcellulose films containing natural polysaccharides by thermal analysis and FTIR spectroscopy. Acta Farm Bonaerense 23:53–57Google Scholar
  7. Cousins SK, Brown RM (1995) Cellulose I microfibril assembly: computational molecular mechanics energy analysis favours bonding by van der Waals forces as initial step in crystalization. Polymer 36:3885–3888CrossRefGoogle Scholar
  8. Crowley MM, Schroeder B, Fredersdorf A, Obara S, Talarico M, Kucera S, McGinity JW (2004) Physicochemical properties and mechanism of drug release from ethyl cellulose matrix tablets prepared by direct compression and hot-melt extrusion. Int J Pharm 269:509–522CrossRefGoogle Scholar
  9. Duarte ARC, Gordillo MD, Cardoso MM, Simplicio AL, Duarte CMM (2006) Preparation of ethyl cellulose/methyl cellulose blends by supercritical antisolvent precipitation. Int J Pharm 311:50–54CrossRefGoogle Scholar
  10. Ethylcellulose polymers technical handbook (2005). Dow Chemical Company, http://www.dow.com/dowwolff/en/pdfs/192-00818.pdf
  11. Flory PJ, Vrij A (1963) Melting points of linear-chain homologs, the normal paraffin hydrocarbons. J Am Chem Soc 85:3548–3553CrossRefGoogle Scholar
  12. Follonier N, Doelker E, Cole ET (1994) Evaluation of hot-melt extrusion as a new technique for the production of polymer-based pellets for sustained release capsules containing high loading of freely soluble drugs. Drug Dev Ind Pharm 20:1323–1339CrossRefGoogle Scholar
  13. Fox TG, Flory PJ (1950) Second order transition temperatures and related properties of polystyrene. I. Influence of molecular weight. J Appl Phys 21:581–591CrossRefGoogle Scholar
  14. Freelon B, Sutharb K, Ilavsky J (2013) A multi-length-scale USAXS/SAXS facility: 10–50 keV small-angle X-ray scattering instrument. J Appl Cryst 46:1508–1512CrossRefGoogle Scholar
  15. French AD (2012) Combining computational chemistry and crystallography for a better understanding of the structure of cellulose. Adv Cacbohyd Chem Biochem 67:19–93CrossRefGoogle Scholar
  16. Gopalan M, Mandelkern L (1967) The effect of crystallization temperature and molecular weight on the melting temperature of linear polyethylene. J Phys Chem 71:3833–3841CrossRefGoogle Scholar
  17. Hughes NE, Marangoni AG, Wright AJ, Rogers MA, Rush JWE (2009) Potential food applications of edible oil organogels. Food Sci Tech 20:470–480CrossRefGoogle Scholar
  18. Ilavsky J (2012) Nika: software for two-dimensional data reduction. J Appl Cryst 45:324–328CrossRefGoogle Scholar
  19. Ilavsky J, Jemian PR (2009) Irena: tool suite for modeling and analysis of small-angle scattering. J Appl Cryst 42:347–353CrossRefGoogle Scholar
  20. Ilavsky J, Jemian PR, Allen AJ, Zhang F, Levine LE, Long GG (2009) Ultra-small-angle X-ray scattering at the advanced photon source. J Appl Cryst 42:469–479CrossRefGoogle Scholar
  21. Ilavsky J, Allen AJ, Levine LE, Zhang F, Jemianc PR, Longa GG (2012) High-energy ultra-small-angle X-ray scattering instrument at the advanced photon source. J Appl Cryst 45:1318–1320CrossRefGoogle Scholar
  22. Isogai A, Atalla RH (1998) Dissolution of cellulose in aqueous NaOH solutions. Cellulose 5:309–319CrossRefGoogle Scholar
  23. Jeffries R (1968) Preparation and properties of films and fibers of disordered cellulose. J Appl Polym Sci 12:425–445CrossRefGoogle Scholar
  24. Jullien R (1987) Aggregation phenomena and fractal aggregates. Contemp Phys 28:477–493CrossRefGoogle Scholar
  25. Knill CJ, Kennedy JF (1998) Cellulosic biomass-derived products. In: Dumitriu S (ed) Polysaccharides: structural diversity and functional versatility. Marcel Dekker, New York, pp 937–956Google Scholar
  26. Koch W (1937) Properties and uses of ethylcellulose. Ind Ing Chem 29:687–690CrossRefGoogle Scholar
  27. Kondo T (1998) Hydrogen bonds in cellulose and cellulose derivatives. In: Dumitriu S (ed) Polysaccharides: structural diversity and functional versatility, 2nd edn. Marcel Dekker, New York, pp 69–98Google Scholar
  28. Kondo T, Sawatari C (1996) A Fourier transform infra-red spectroscopic analysis of the character of hydrogen bonds in amorphous cellulose. Polymer 37:393–399CrossRefGoogle Scholar
  29. Maki R, Suihko E, Korhonen O, Pitkanen H, Niemi R, Lehtonen M, Ketolainen J (2006) Controlled release of saccharides from matrix tablets. Eur J Pharm Biopharm 62:163–170CrossRefGoogle Scholar
  30. Meakin P, Jullien R (1985) Structural readjustment effects in cluster–cluster aggregation. J Phys France 46:1543–1552CrossRefGoogle Scholar
  31. Moore WR, Brown AM (1959) Viscosity-temperature relationships for dilute solutions of cellulose derivatives II. Intrinsic viscosities of ethyl cellulose. J Colloid Sci 14:343–353CrossRefGoogle Scholar
  32. Morris ER, Cutler AN, Ross-Murphy SB, Rees DA (1981) Concentration and shear rate dependence of viscosity in random coil polysaccharide solutions. Carbohyd Polym 1:5–21CrossRefGoogle Scholar
  33. Nelson ML, O’Conner RT (1964) Relation of certain infrared bands to cellulose crystallinity and crystal lattice type. Part I. Spectra of lattice types I, 11, I11 and of amorphous cellulose. J Appl Polym Sci 8:1311–1324CrossRefGoogle Scholar
  34. O’sullivan AC (1997) Cellulose: the structure slowly unravels. Cellulose 4:173–207CrossRefGoogle Scholar
  35. Overney RM, Buenviaje C, Luginbuhl R, Dinelli F (2000) Glass and structural transitions measured at polymer surfaces on the nanoscale. J Therm Anal Cal 59:205–225CrossRefGoogle Scholar
  36. Perez S, Samain D (2010) Structure and engineering of celluloses. Adv Cacbohyd Chem Biochem 64:26–116Google Scholar
  37. Rekhi GS, Jambhekar SS (1995) Ethylcellulose: a polymer review. Drud Dev Ind Pharm 21:61–77CrossRefGoogle Scholar
  38. Repka MA et al (2007) Pharmaceutical applications of hot-melt extrusion: part II. Drug Dev Ind Pharm 33:1043–1057CrossRefGoogle Scholar
  39. Roos Y, Karel M (1991) Water and molecular weight effects on glass transitions in amorphous carbohydrates and carbohydrate solutions. J Food Sci 56:1676–1681CrossRefGoogle Scholar
  40. Roudaut G, Simatos D, Champion D, Contreras-Lopez E, Meste ML (2004) Molecular mobility around the glass transition temperature: a mini review. Innov Food Sci Emerg Tech 5:127–134CrossRefGoogle Scholar
  41. Rowe RC, Kotaras AD, White EFT (1984) An evaluation of the plasticizing efficiency of the dialkyl phthalates in ethyl cellulose films using the torsional braid pendulum. Int J Pharm 22:57–62CrossRefGoogle Scholar
  42. Roy D, Semsarilar M, Guthrie JT, Perrier S (2009) Cellulose modification by polymer grafting: a review. Chem Soc Rev 38:2046–2064CrossRefGoogle Scholar
  43. Sakellariou P, Rowe RC, White EFT (1985) The thermo mechanical properties and glass transition temperatures of some cellulose derivatives used in film coating. Int J Pharm 27:267–277CrossRefGoogle Scholar
  44. Sandford PA, Cottrell IW, Pettitt DJ (1984) Microbial polysaccharides: new products and their commercial applications. Pure Appl Chem 56:879–892CrossRefGoogle Scholar
  45. Schaefer DW, Hurd AJ (1990) Growth and structure of combustion aerosols fumed silica. Aerosol Sci Tech 12:876–890CrossRefGoogle Scholar
  46. Sinha SK, Freltoft T, Kjems J (1984) Observation of power law correlations in silica-particle aggregates by small-angle neutron scattering. In: Family F, Landau DP (eds) Kinetics of aggregation and gelation. North-Holland Physics Publishing, Amsterdam, pp 87–90CrossRefGoogle Scholar
  47. Skillas G et al (2002) Relation of the fractal structure of organic pigments to their performance. J Appl Phys 91:6120–6124CrossRefGoogle Scholar
  48. Soares JP, Santos JE, Chierice GO, Cavalheiro ETG (2004) Thermal behavior of alginic acid and its sodium salt. Eclet Quim 29:57–63CrossRefGoogle Scholar
  49. Tarvainen M et al (2003) Enhanced film-forming properties for ethyl cellulose and starch acetate using n-alkenyl succinic anhydrides as novel plasticizers. Eur J Pharm Sci 19:363–371CrossRefGoogle Scholar
  50. Torres FE, Russel WB, Schowalter WR (1991) Simulations of coagulation in viscous flows. J Colloid Interface Sci 145:51–73CrossRefGoogle Scholar
  51. Wada M (2002) Lateral thermal expansion of cellulose I and I III Polymorphs. J Polym Sci B: Polym Phys 40:1095–1102CrossRefGoogle Scholar
  52. Wada M, Hori R, Kim U-J, Sasaki S (2010) X-ray diffraction study on the thermal expansion behavior of cellulose Ib and its high-temperature phase. Polym Deg Stab 95:1330–1334CrossRefGoogle Scholar
  53. Ward TC (1981) Molecular weight and molecular weight distributions in synthetic polymers. J Chem Edu 58:867–879CrossRefGoogle Scholar
  54. Witten TA, Sander LM (1983) Diffusion-limited aggregation. Phys Rev B 27:5686–5697Google Scholar
  55. Yu DG, Yang XL, Huang WD, Liu J, Wang YG, Xu H (2006) Tablets with material gradients fabricated by three-dimensional printing. J Pharm Sci 96:2446–2456CrossRefGoogle Scholar
  56. Zetzl AK, Marangoni AG, Barbut S (2012) Mechanical properties of ethylcellulose oleo gels and their potential for saturated fat reduction in frankfurters. Food Funct 3:327–337CrossRefGoogle Scholar
  57. Zuluaga R, Putaux JL, Cruz J, Vélez J, Mondragon I, Gañán P (2009) Cellulose microfibrils from banana rachis: effect of alkaline treatments on structural and morphological features. Carbohyd Polym 76:51–59CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2014

Authors and Affiliations

  • M. Davidovich-Pinhas
    • 1
  • S. Barbut
    • 1
  • A. G. Marangoni
    • 1
  1. 1.University of GuelphGuelphCanada

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