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Chapter 8 Chemiluminescence of cellulose and paper Matija Strli?, Jozef Rychly, Olivier Haillant, Drago Ko?ar, Jana Kolar 8.1 Introduction Studies of chemiluminescence have been shown to be an extremely relevant method in polymer degradation studies.1 The light is usually, although not exclusively, a consequence of an exothermal reaction, such as oxidation reactions involving atmospheric oxygen. Studies of oxidative degradation have thus been in the focus of polymer degradation research using chemiluminescence ever since Ashby reported that polymers emit weak light during heating in air in 1961.2 As oxidative degradation is the dominant degradation pathway in alkaline cellulose and paper, chemiluminometry may well provide relevant information on kinetics of the process. Contemporary luminometers allow measurements at ambient and even lower temperatures.3 A measurement takes no longer than a few minutes. Since light is measured while the very reactions take place, the method is non-invasive and it can be, in principle, also non-destructive. Considering that the classical Arrhenius accelerated degradation studies are time- and work-intensive, benefits of the chemiluminometric approach are obvious. The potential of chemiluminometry in paper stability studies was recognized by Kelly et al. already in 1979.4 The authors cycled moist and dry air above a paper sample (containing 8% fillers, including 3% TiO2) at 70 °C (Figure 8.1), and obtained a repeatable behaviour: on each switch to moist atmosphere a sharp CL peak appeared and the signal then dropped below the level of CL in dry atmosphere. The hypothesis was put forward that water-absorption-induced swelling leads to bond-scission, and thus to enhanced oxidation. As we shall see later in this Chapter, the effect of water on chemiluminescence phenomena is fairly complex and most probably involves both physical and chemical phenomena. The authors also attempted a kinetic evaluation of the observed phenomena and des