Page Header Logo
TEI of Athens eJournals

Pure cellulose paper ageing in sealed vessels. Autocatalytic depolymerization model revisited

Spiros Zervos, Konstantinos Choulis, Georgios Panagiaris


Purpose - In the framework of the EU funded INVENVORG project (Thales Research Funding Program – NRSF), the natural and artificial ageing of bone, wood, textiles, parchment and paper were investigated.

Design/methodology/approach - In this work, the results of accelerated ageing on pure cellulose paper in sealed vessels are reported. The properties studied include the degree of polymerization (which was converted to the percentage of broken glyosidic bonds), the tearing resistance, the pH and the L* and b* coordinates of the CIEL*a*b* color system. Ageing was performed in sealed vessels at 90°C και 76% RH for periods of 20, 40, 60, 80, 100, 120 and 140 days.

Findings - The results indicated an overall deterioration of all paper properties, which accelerates with time because of the production of volatile acidic species (autocatalysis). The evolution of paper properties through time was modeled efficiently by use of the equations proposed by Zervos and Moropoulou (2005) for the autocatalytic acid hydrolysis of pure cellulose paper, which were shown that also apply for following the changes of tearing resistance. The applicability of the model equations was also verified for other paper properties, such as the percentage of broken bonds (δ%) and the L* and b* coordinates of the CIEL*a*b* color system.


Cellulose ageing model; autocatalysis; tearing resistance; pH; optical properties; sealed vessels


Ekenstam, A (1936). The behaviour of cellulose in mineral acid solutions. Kinetic study of the decomposition of cellulose in acid solution (Über das Verhalten der Cellulose in Mineralsäure-Lösungen, II. Mitteil.: Kinetisches Studium des Abbaus der Cellulose in Säure-Lösungen). Berichte der Deutschen Chemischen Gesellschaft 69: 553-559.

Krassig, H & Kitchen, W (1961). Factors influencing tensile properties of cellulose fibers. Journal of Polymer Science 51: 123-172.

Michie, RIC, Sharples, A & Walter, AA (1961). The nature of acid-sensitive linkages in cellulose. Journal of Polymer Science 51: 131-140.

Fung, DPC (1969). Kinetics and mechanism of the thermal degradation of cellulose. TAPPI Journal 52(2): 319-321.

Shafizadeh, F & Bradbury, AGW (1979). Thermal degradation of cellulose in air and nitrogen at low temperatures. Journal of Applied Polymer Science 23: 1431-1442.

Marx-Figini, M & Coun-Matus, M (1981). On the kinetics of hydrolytic degradation of native cellulose. Die Makromolekulare Chemie 182(12): 3603-3616.

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. Washington, DC, American Chemical Society, pp. 329-347.

Fellers, C, Iversen, T, Lindstrom, T, Nilsson, T & Rigdahl, M (1989). Ageing/degradation of paper, a literature survey. FoU-projektet for papperskonservering. Stockholm, FoU-projektet for papperskonservering.

Lee, SB, Bogaard, J & Feller, RL (1989). Damaging effects of visible and near-ultraviolet radiation on paper. In: Zeronian, SH & Needles, HL (eds.) Historic textile and paper materials II. Conservation and characterization. ACS Symposium Series 410. Washington, DC, American Chemical Society, pp. 54-62.

Emsley, AM & Stevens, GC (1994). Kinetics and mechanisms of the low-temperature degradation of cellulose. Cellulose 1: 26-56.

Zou, X, Gurnagul, N, Uesaka, T & Bouchard, J (1994). Accelerated aging of papers of pure cellulose: mechanism of cellulose degradation and paper embrittlement. Polymer Degradation and Stability 43: 393-402.

Hill, DJT, Le, TT, Darveniza, M & Saha, T (1995). A study of degradation of cellulosic insulation materials in a power transformer, part 1. Molecular weight study of cellulose insulation paper. Polymer Degradation and Stability 48: 79-87.

Zou, X, Uesaka, T & Gurnagul, N (1996). Prediction of paper permanence by accelerated aging I. Kinetic analysis of the aging process. Cellulose 3: 243-267.

Kolar, J, Strlič, M, Malešič, J, Lemaire, J & Fromageot, D (2005). Photooxidative degradation. In: Strlič, M & Kolar, J (eds.) Ageing and stabilization of paper. Ljubljana, National and University Library, pp. 149-162.

Gilbert, R, Jalbert, J, Tétreault, P, Morin, B & Denos, Y (2009). Kinetics of the production of chain-end groups and methanol from the depolymerization of cellulose during the ageing of paper/oil systems. Part 1: Standard wood kraft insulation. Cellulose 16(2): 327-338.

Zervos, S (2010). Natural and accelerated ageing of cellulose and paper: A literature review. In: Lejeune, A & Deprez, T (eds.) Cellulose: Structure and Properties, Derivatives and Industrial Uses. New York, Nova Publishing, pp. 155-203.

Emsley, AM, Heywood, RJ, Ali, M & Eley, CM (1997). On the Kinetics of Degradation of Cellulose. Cellulose 4: 1-5.

Heywood, RJ, Stevens, GC, Ferguson, C & Emsley, AM (1999). Life assessment of cable paper using slow thermal ramp methods. Thermochimica Acta 332: 189-195.

Calvini, P (2005). The influence of the leveling-off degree of polymerization on the kinetics of cellulose degradation. Cellulose 12: 445–447.

Ding, H-Z & Wang, ZD (2005). Modelling the ageing of cellulose insulation in power transformers. 3rd IEE international conference on reliability of transmission and distribution networks (RTDN 2005), London, UK, IEE Conference Publication, 508: 315-319.

Zervos, S & Moropoulou, A (2005). Cotton cellulose ageing in sealed vessels. Kinetic model of autocatalytic depolymerization. Cellulose 12(5): 485-496.

Calvini, P & Gorassini, A (2006). On the rate of paper degradation: lessons from the past. Restaurator 27: 275–290.

Calvini, P, Gorassini, A & Merlani, L (2007). Autocatalytic degradation of cellulose paper in sealed vessels. Restaurator 28(1): 47–54.

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(3): 171–181.

Ding, H-Z & Wang, ZD (2008a). Author response to the comments by P. Calvini regarding the article “On the degradation evolution equations of cellulose” by H.-Z. Ding and Z. D. Wang. Cellulose 15(2): 229-237.

Ding, H-Z & Wang, ZD (2008b). On the degradation evolution equations of cellulose. Cellulose 15(2): 205-224.

Calvini, P (2012). The role of the Ekenstam equation on the kinetics of cellulose hydrolytic degradation. Cellulose 19(2): 313-318.

Calvini, P (2014). On the meaning of the Emsley, Ding & Wang and Calvini equations applied to the degradation of cellulose. Cellulose 21(3): 1127-1134.

Zervos, S, Choulis, K & Panagiaris, G (2014). Experimental design for the investigation of the environmental factors effects on organic materials (Project INVENVORG). The case of paper. Procedia - Social and Behavioral Sciences 147: 39–46.

Greenspan, L (1977). Humidity fixed points of binary saturated aqueous solutions. Journal of research of the National Bureau of Standards. A, Physics and chemistry 81A (1): 89-96.

TAPPI T 402 om-88 (1988). Standard conditioning and testing atmospheres for paper, board, pulp handsheets and related products.

TAPPI T 529 om-04 (2004). Surface pH measurement of paper

ASTM D 1795-96 (R2001). Standard test method for intrinsic viscosity of cellulose.

Shahani, C, Lee, SB, Hengemihle, FH, Harrison, G, Song, P, Sierra, ML, Ryan, CC & Weberg, N (2001). Accelerated aging of paper: I. Chemical analysis of degradation products. II. Application of Arrhenius relationship. III. Proposal for a new accelerated aging test: ASTM research program into the effect of aging on printing and writing papers. Washington, DC, Library of Congress.

Shahani, CJ & Harrison, G (2002). Spontaneous formation of acids in the natural aging of paper. In: Daniels, V, Donithorne, A & Smith, P (eds.) Works of Art on paper, books, documents and photographs. Techniques and conservation. Congress of the International institute for Conservation, Baltimore, MD. Int. Inst. For Conservation: 189–192.

Lattuati-Derieux, A, Bonnassies-Termes, S & Lavédrine, B (2006). Characterisation of compounds emitted during natural and artificial ageing of a book. Use of headspace-solid-phase microextraction/gas chromatography/mass spectrometry. Journal of Cultural Heritage 7 123–133.

Dupont, A-L, Egasse, C, Morin, A & Vasseur, F (2007). Comprehensive characterisation of cellulose- and lignocellulosedegradation products in aged papers: Capillary zone electrophoresis of low-molar mass organic acids, carbohydrates, and aromatic lignin derivatives. Carbohydrate Polymers 68 1–16.

Zervos, S & Moropoulou, A (2006). Methodology and criteria for the evaluation of paper conservation interventions. Literature review. Restaurator 27(4): 219-274.

Full Text: PDF

DOI: 10.26265/jiim.v4i2.4419


  • There are currently no refbacks.

The application for presenting electronic journals TEI developed within subproject 2 "electronic publishing service" the Act "Development Services Digital Library of TEI" and financed by the operational program "Digital Convergence", NSRF 2007-2013.