Cellulose

, Volume 15, Issue 2, pp 205–224 | Cite as

On the degradation evolution equations of cellulose

Article

Abstract

Cellulose degradation is usually characterized in terms of either the chain scission number or the scission fraction of cellulose unit as a function of degree of polymerisation (DP) and cellulose degradation evolution equation is most commonly described by the well known Ekenstam equations. In this paper we show that cellulose degradation can be best characterized either in terms of the percentage DP loss or in terms of the percentage tensile strength (TS) loss. We present a new cellulose degradation evolution equation expressed in terms of the percentage DP loss and apply it for having a quantitative comparison with six sets of experimental data. We develop a new kinetic equation for the percentage TS loss of cellulose and test it with four sets of experimental data. It turns out that the proposed cellulose degradation evolution equations are able to explain the real experimental data of different cellulose materials carried out under a variety of experimental conditions, particularly the prolonged autocatalytic degradation in sealed vessels. We also develop a new method for predicting the degree of degradation of cellulose at ambient conditions by combining the master equation representing the kinetics of either percentage DP loss or percentage TS loss at the lowest experimental temperature with Arrhenius shift factor function.

Keywords

Cellulose Degradation Kinetics Modelling Degree of polymerisation Tensile strength Percentage loss Time–temperature superposition Arrhenius activation energy 

References

  1. Arney JS, Noval CL (1982) Accelerated aging of paper. The influence of acidity on the relative contribution of oxygen-independent and oxygen-dependent processes. Tappi J 65:113–115Google Scholar
  2. Barański A, Łagan JM, Łojewski T (2006) The concept of mixed-control mechanisms and its applicability to paper degradation studies. e-PS 3:1–4Google Scholar
  3. Bouchard J, Méthot M, Jordan B (2006) The effects of ionizing radiation on the cellulose of woodfree paper. Cellulose 13:601–610CrossRefGoogle Scholar
  4. Calvini P (2005) The influence of levelling-off degree of polymerisation on the kinetics of cellulose degradation. Cellulose 12:445–447CrossRefGoogle Scholar
  5. Calvini P, Gorassini A (2006) On the rate of paper degradation: lessons from the past. Restaurator 27(4):275–290CrossRefGoogle Scholar
  6. Chen SL, Lucia LA (2003) Improved method for evaluation of cellulose degradation. J Wood Sci 49:285–288CrossRefGoogle Scholar
  7. Daruwalla EH, Narsian MG (1966) Detection and identification of acid-sensitive linkages in cellulose fiber substances. Tappi J 49(3):106–111Google Scholar
  8. Ding H-Z, Wang ZD (2007) Time–temperature superposition method for predicting the permanence of paper by extrapolating accelerated ageing data to ambient conditions. Cellulose 14:171–181CrossRefGoogle Scholar
  9. Ekenstam A (1936) The behaviour of cellulose in mineral acid solutions: kinetic study of the decomposition of cellulose in acid solutions. BER 69:540–553Google Scholar
  10. Emsley AM, Stevens GC (1994) Kinetics and mechanisms of the low temperature degradation of cellulose. Cellulose 1:26–56CrossRefGoogle Scholar
  11. Emsley AM, Heywood RJ, Ali M, Eley CM (1997) On the kinetics of degradation of cellulose. Cellulose 4:1–5CrossRefGoogle Scholar
  12. Emsley AM, Xiao X, Heywood RJ, Ali M (2000a) Degradation of cellulosic insulation in power transformers. Part 3: effects of oxygen and water on ageing in oil. IEE Proc Sci Meas Technol 147(3):115–119CrossRefGoogle Scholar
  13. Emsley AM, Heywood RJ, Ali M, Xiao X (2000b) Degradation of cellulosic insulation in power transformers. Part 4: effects of ageing on the tensile strength of paper. IEE Proc Sci Meas Technol 147(6):285–290CrossRefGoogle Scholar
  14. Feller RL, Lee SB, Bogaard J (1986) The kinetics of cellulose deterioration. In: Needles HL, Zeronian SH (eds) Historic textile and paper materials: conservation and characterization. Advances in chemistry series 212. American Chemical Society, Philadelphia, USA, pp 329–346Google Scholar
  15. Fung DPC (1969) Kinetics and mechanism of the thermal degradation of cellulose. Tappi J 52:319–321Google Scholar
  16. Gasser HP, Huser J, Krause C, Dahinden V, Emsley AM (1999) Determining the ageing parameters of cellulosic insulation in a transformer. In: Eleventh international symposium on high voltage engineering (IEE Conf. Publ. No. 467), London, 23–27 August 1999, pp 4.143–4.147Google Scholar
  17. Gillen KT, Bernstein R, Derzon DK (2005a) Evidence of non-Arrhenius behaviour from laboratory aging and 24-years field aging of polychloroprene rubber materials. Poly Deg Stab 87:57–67CrossRefGoogle Scholar
  18. Gillen KT, Bernstein R, Celina M (2005b) Non-Arrhenius behavior for oxidative degradation of chlorosulfonated polyethylene materials. Poly Deg Stab 87:335–346CrossRefGoogle Scholar
  19. Hansen AC, Baker-Jarvis J (1990) A rate-dependent kinetic theory of fracture for polymers. Inter J Fracture 44:221–231Google Scholar
  20. Heywood RJ, Stevens GC, Ferguson C, Emsley AM (1999) Life assessment of cable paper using slow thermal ramp method. Thermochim Acta 332:189–195CrossRefGoogle Scholar
  21. Hill DJT, Le TT, Darveniza M, Saha T (1995) A study of degradation of cellulosic insulation materials in a power transformer. Part 2: tensile strength of cellulose insulation paper. Polym Deg Stab 49:429–435CrossRefGoogle Scholar
  22. Hon DNS (1985) Mechanochemistry of cellulosic materials. In: Kennedy JF, Phillips GO, Wedlock DJ, Williams PA (eds) Cellulose and its derivatives: chemistry, biochemistry and applications, chapter 6. Ellis Horwood Limited, Chichester, UK, pp 71–86Google Scholar
  23. Johansson EE, Lind J, Ljunggren S (2000) Aspects of the chemistry of cellulose degradation and the effect of ethylene glycol during ozone delignification of Kraft pulps. J Pulp Pap Sci 26:239–244Google Scholar
  24. Krassig H, Kitchen W (1961) Factors influencing tensile properties of cellulose fibers. J Polym Sci 51:123–172Google Scholar
  25. Kukensko VS, Tamuzs VP (1981) Fracture micromechanics of polymer materials. Martinus Nijhoff Publishers, Boston, MAGoogle Scholar
  26. Margutti S, Conio G, Calvini P, Pedemonte E (2001) Hydrolytic and oxidative degradation of paper. Restaurator 22:67–83CrossRefGoogle Scholar
  27. McCrady E (1996) Effect of metals on paper: a literature review. Alkaline Paper Advocate, vol 9(1), MayGoogle Scholar
  28. McShane CP, Corkran JL, Rapp KJ, Luksich J (2003) Aging of paper insulation retrofilled with natural ester dielectric fluid. IEEE 2003 annual report conf. on electrical insulation and dielectric phenomena. Albuquerque, USA, pp 124–127Google Scholar
  29. Moser HP, Dahinden V (1987) Transformerboard II. H. Weidmann AG, CH-8640 RapperswilGoogle Scholar
  30. Petrov VA (1984) Lifetime-under-load of solid subjected to stresses below the breaking value. Sov Phys Solid State 26:1283–1284Google Scholar
  31. Shafizadeh F, Bradbury AGW (1979) Thermal degradation of cellulose in air and nitrogen at low temperatures. J Appl Polym Sci 23:1431–1442CrossRefGoogle Scholar
  32. Sharples A (1954) The hydrolysis of cellulose. Part 1. The fine structure of Egyptian cotton. J Polym Sci 13:393–401CrossRefGoogle Scholar
  33. Sharples A (1971) Degradation of cellulose and its derivatives. A. Acid hydrolysis and alcoholysis. In: Bikales NM, Segal L (eds) Cellulose and cellulose derivatives, vol V, Pt V. Wiley-Interscience, New York, pp 991–1006Google Scholar
  34. Soares S, Ricardo N, Heatley F, Rodrigues E (2001) Low temperature thermal degradation of cellulosic insulating paper in air and transformer oil. Polym Int 50:303–308CrossRefGoogle Scholar
  35. Strlič M, Kolar J, Pihlar B, Rychlý J, Matisová-Rychlá L (2001) Initial degradation process of cellulose at elevated temperatures revisited-chemiluminescence evidence. Polym Deg Stab 72:157–162CrossRefGoogle Scholar
  36. Testa G, Sardella A, Rossi E, Bozzi C, Seves A (1994) The kinetics of cellulose fiber degradation and correlation with some tensile properties. Acta Polymer 45:47–49CrossRefGoogle Scholar
  37. Williams JC, Fowler CS, Lyon MS, Merrill TL (1977) Metallic catalysts in the oxidative degradation of paper. Advances in chemistry series, ACS 164, pp 37–61Google Scholar
  38. Zervos S, Moropoulou A (2005) Cotton cellulose ageing in sealed vessels. Kinetic model of autocatalytic depolymerization. Cellulose 12:485–496CrossRefGoogle Scholar
  39. Zhurkov SN, Korsukov VE (1974) Atomic mechanism of fracture of solid polymers. J Polym Sci: Polym Phys 12:385–398CrossRefGoogle Scholar
  40. Zou X, Gurnagul N, Uesaka T, Bouchard J (1994) Accelerated ageing of papers of pure cellulose: mechanism of cellulose degradation and paper embrittlement. Polym Deg Stab 43:393–402CrossRefGoogle Scholar
  41. Zou X, Uesaka T, Gurnagul N (1996) Prediction of paper permanence by accelerated ageing: Part 1 kinetic analysis of the aging process. Cellulose 3:243–267CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2007

Authors and Affiliations

  1. 1.School of Electrical and Electronic EngineeringThe University of ManchesterManchesterUK

Personalised recommendations