Abstract
The validity of accelerated aging tests to predict and rank papers on their permanence has been under question, preventing the development of performance-based standards for permanent paper. We conducted a general kinetic analysis to investigate the aging process of paper. A general kinetic model is proposed to describe the depolymerization of cellulose. Experimentally it was shown that in the case of aging, cellulose degradation follows classic first-order kinetics as a special case of our general kinetic model. The Arrhenius equation was critically re-examined for the case of a multiple reaction system. It was shown analytically that the Arrhenius equation is still applicable when certain conditions are met. This was convincingly supported by experimental results. We also analysed the dependence of the degradation rate on the moisture content and hydrogen ion concentration. By conducting systematic experiments on these two factors, a general and quantitative relationship was established to explain the contribution of each factor and their interactions. Finally, based on this kinetic analysis, the effects of storage conditions on the life expectancy of paper were estimated.
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Adelstein, P. Z. and McCrea, J. L. (1977) Dark image stability of diazo film.J. Appl. Photogr. Eng. 3, 173–178.
Agarwal, N., McKean, W. T. and Gustafson, R. R. Cellulose degradation kinetics in alkaline pulping.Proc. 6th Intl. Symp. Wood Pulping Chem., Melbourne, Australia, 1991, pp. 213–220.
Arney, J. S. and Jacobs, A. J. (1979) Accelerated aging of paper: the relative importance of atmospheric oxidation.Tappi J. 62(7), 89–91.
Arney, J. S. and Jacobs, A. J. (1982) Accelerated aging of paper: the influence of acidity on the relative contribution of oxygen-independent and oxygen-dependent processes.Tappi J. 65(3), 113–115.
Baer, N. S. and Indicator, N. (1977) Use of the Arrhenius equation in multi-component system. inPreservation of Paper and Textile of Historic and Artistic Values. Am. Chem. Soc. Symp. Ser. No. 164, pp. 336–351.
Bansa, H. (1992) Accelerated aging tests in conservation research: some ideas for future methods.Restaurator 13, 147–157.
Bard, C. C., Larson, G. W., Hammond, H. and Packard, C. (1980) Predicting long-term dark storage dye stability characteristics of color photographic products from short-term tests.J. Appl. Photogr. Eng. 6(2), 42–45.
Barrow, W. J. and Sproull, R. C. (1959) Permanence in book papers.Science 129(3356), 1075.
BeMiller, J. N. (1967)Adv. Carbohydr. Chem. 22, 25.
Boyd, R. H. (1966) Theoretical depolymerization kinetics. III. The effect of molecular weight distribution in degrading polymers undergoing random-scission initiation.J. Chem. Phys. 45(3), 778–781.
Browning, B. L. and Wink, W. A. (1969) Studies on permanence and durability of paper: I. Prediction of paper permanence.Tappi J. 51(4), 156–163.
Cowan, W. F. (1972) Why not ‘zero-span’ testing of paper tensile strength.Pulp Paper 46(3), 86.
Daruwalla, E. H. and Narsian, M. G. (1966) Detection and identification of acid-sensitive linkages in cellulose fibre substances.Tappi J. 49(3), 106.
Ekamstam, A. (1936) The behaviour of cellulose in mineral acid solutions: kinetic study of the decomposition of cellulose in acid solution.Ber. Deutschen Chem. Gesellschaft 69, 553.
Emsley, A. M. and Stevens, G. C. (1994) Kinetics and mechanisms of the low-temperature degradation of cellulose.Cellulose 1(1), 26–56.
Erhard, D. and Mecklenburg, M. (1994) Accelerated vs. natural aging: effect of aging conditions on the aging process of cellulose.Proc. 4th Symp. on Materials Issues in Art and Archaeology, pp 247–270.
Erhard, D., von Endt, D. and Hopwood, W. (1987) The comparison of accelerated aging conditions through the analysis of extracts of artificially aged papers.Preprints of the 1987 Annual Conference of the American Institute for Conservation, Vancouver, B.C., pp. 43–55.
Erhard, D., von Endt, D. and Hopwood, W. (1988) Paper degradation: a comparison of industrial and archival concerns. inPaper Preservation: Current Issues and Recent Developments, (P. Luner, ed.) TAPPI PRESS, Technology Park, Atlanta, 1988, pp. 63–68.
Feller, R. L., Lee, S. B. and Bogaard, J. (1986) The kinetics of cellulose deterioration. inAdvances in Chemistry, Am. Chem. Soc. Symp. Ser. No. 212, pp. 329–347.
Freudenberg, K., Kuhn, W., Durr, W., Bolz, F. and Steinbrunm, G. (1930) Hydrolysis of polysaccharides.Ber. Deutschen Chem. Gesellschaft 63, 1510.
Graminski, E. L., Parks, E. J. and Toth, E. E. (1979) The effect of temperature and moisture on the accelerated aging of paper. inDurability of Macromolecular Materials (R. K. Eby, ed.)Am. Chem. Soc. Symp. Ser. No. 95, 1979, Chap. 24, pp. 342–355.
Gray, G. G. (1969) Accelerated aging study: comparing kinetic rates vs. Tappi Standard 453.Tappi J. 52(2), 325–334.
Gurnagul, N., Page, D. H. and Paice, M. G. (1992) The effect of cellulose degradation on the strength of wood pulp fibres.Nordic Pulp & Paper Res. J. (3), 152–154.
Hall, G. (1926) Permanence of paper.Tech. Assoc. Papers IX: 92.
Hernadi, S. (1976) Thermal aging in oxygen of paper made from cellulose at different degrees of beating.Svensk Papperstendning 79(13), 418–423.
Immergut, E. H., Schurz, J. and Mark, H. (1953)Monatsh. Chem. 84(2), 219–249.
ISO Standard 5630-1986 (E), Paper and board — accelerated aging — Part 3: Moist treatment at 80 °C and 65% relative humidity, 1986.
Kuhn, W. (1930) On the kinetics of reduction of high molecular weight chains.Ber. Deutschen Chem. Gesellschaft 63, 1503.
Luner, P. (1969) Paper permanence.Tappi J. 52(5): 796–805.
Luner, P. (1988) Evaluation of paper permanence.Wood Sci. Technol. 22, 81–97.
Major, W. D. (1958) The degradation of cellulose in oxygen and nitrogen at high temperature.Tappi J. 41(9), 530.
McBurney, L. F. (1954)Cellulose and Cellulose Derivatives. Part I (E. Ott, H. M. Spurlin and U. W. Grafflin, eds.) New York: Wiley-Interscience, pp. 99–176.
Millet, M. A., Wester, L. J. and Booth, J. J. (1967) Accelerated aging of cellulosic materials: design and application of a heating chamber.Tappi J. 50(11), 74A.
Parks, E. J. and Hebert, R. L. (1972) Accelerated aging of laboratory handsheets: reflectance, moisture regain, sonic modulus and differential thermal analysis, NBS Report 10-687, NTIS COM 75 10602.
Priest, D. J. (1994) Artificial aging of paper: correlation with natural aging.Proc. ASTM Workshop on the Effects of Aging on Printing and Writing Papers, Philadelphia, PA, pp. 50–60.
Priest, D. J. and Stanley, J. (1993) The permanence of papers containing modern high yield pulps.Transactions of the 10th Fundamental Research Symposium — Oxford, Vol. 2, Mechanical London: Engineering Publications Ltd. pp. 1515–1553.
Roberson, D. (1976) The evaluation of paper permanence and durability.Tappi J. 59(12), 63–69.
Saad, S. M. and El-Kholy, A. E. (1980) Kinetic investigation of thermal aging of unbleached Egyptian bagasse paper-pulp.Holzforschung 34, 147–149.
Saad, S. M., El-Answar, J. M. and Metwally, N. E. (1979) Evaluation of thermal aging of Egyptian unbleached kraft bagasse pulp. Part II: Effect of aging on chemical and mechanical properties.Holzforschung 33, 125–128.
Scandinavian Pulp, Paper and Board Testing Standard (1962)Viscosity of Cellulose in Cupriethylenediamine (CED) Solution, SCAN-C15: 65.
Schroff, D. H. and Stannet, A. W. (1985) Review of paper aging in power transformers.IEE Proc. C., G. B. 132(6), 312–319.
Sharples, A. (1954) The hydrolysis of cellulose. Part II: Acid-sensitive linkages in Egyptian cottons.J. Polym. Sci. 13, 393.
Sharples, A. (1957) The hydrolysis of cellulose and its relationship to structure.Trans. Faraday Soc. 53, 1003–1009.
Sharples, A. (1971) Acid hydrolysis and Alcoholysis, inHigh Polymer, Degradation of Cellulose and Its Derivatives. Part V. 2nd Ed., (N. M. Bikales and I. Segal, eds.) New York: Wiley-Interscience.
Shahani, C. J. (1994) Accelerated aging of paper: can it really foretell the permanence of paper?Proc. ASTM Workshop on the Effects of Aging on Printing and Writing Papers, Philadelphia, PA, pp. 120–139.
Steiger, T. H. (1958) The Arrhenius equation in accelerated aging.American Dyestuff Report 46(9), 287–290.
Strofer-Hua, E. (1990) Experimental measurement: interpreting extrapolation and prediction by accelerated aging.Restaurator 11, 254–266.
TAPPI Provisional Method T 453 pm-85Effect of Dry Heat on Properties of Paper (1985a).
TAPPI Provisional Method T 544 pm-85Effect of Moist Heat on Properties of Paper and Board (1985b).
Zou, X., Gurnagul, N., Uesaka, T. and Bouchard, J. (1994) Accelerated aging of papers of pure cellulose: mechanism of cellulose degradation and paper embrittlement.Polym. Degrad. and Stabil. 43(3), 393–402.
Zou, X., Gurnagul, N. and Uesaka, T. (1993) The role of lignin in the mechanical permanence of paper. Part I: Effect of lignin content.J. Pulp and Paper Sci. 19(6), J235–239.
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Zou, X., Uesaka, T. & Gurnagul, N. Prediction of paper permanence by accelerated aging I. Kinetic analysis of the aging process. Cellulose 3, 243–267 (1996). https://doi.org/10.1007/BF02228805
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DOI: https://doi.org/10.1007/BF02228805