Oxyluminescence

Polymers at elevated temperatures luminesce owing to oxidation. When polymers are heated in air or an oxygen atmosphere at high temperature, light emission caused by oxidation is observed as a function of temperature. This phenomenon is called oxyluminescence (OL). The OL curves can be attributed to the degradation of each polymer so that the amount of light emission usually increases with increase in temperature. 

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Electrochemiluminescence Emission occurring in solution, from an electronically excited state produced by high-energy electron transfer reactions Electrogenerated chemiluminescence Emission produced at an electrode surface Oxyluminescence Emission from polymers caused by oxidative processes (presence of oxygen is required)... 

Numerous oxyluminescences, which con be obtained in organic chemistry by rising ozone, open new possibilities for ozone assay, and preliminary results show that a suitable method may be found. Numerical values show the sensitivity of this technique. Small paper disks about the size of confetti and containing no more than 1 y of luminol permit measurements which take only a few minutes. Relatively simple electronic devices permit translation of th se luminescence phenomena into doses (percentages). 

Attempts to classify the chemiluminescence reactions (4, have shown that the oxidants capable of producing oxyluminescence are but few in number and that ozone plays an outstanding role in the excitation of organic compounds. 

In the experiments described the authors have tried to find out whether it is possible to determine ozone quantitatively by a method based upon organic oxyluminescence phenomena. 

Ozone in Presence of Mineral Compounds. With the metalloids, Baker and Strutt (1) have reported an orange oxyluminescence with iodine and with sulfur (which shows a continuous spectrum from 2300 to 4800 A., with a band spectrum from 2300 to 2600), the ultraviolet spectrum here having been studied by Zabiezynski and Orlowski (38). 

Chemiluminescence is also shown with a few simple mineral compounds. Otto (21) expressed the opinion that, if ozone causes a luminescence in the presence of water, it acts upon impurities therein. Hydrogen sulfide gives rise to an ultraviolet chemiluminescence with ozone (Zabiezynski and Orlowski, 33). Several oxygen compounds of nitrogen, especially nitric oxide, show, under the action of ozone, a spectrum different from that of active nitrogen [Morren (20), Sarrasin (23), Strutt (26), Knauss and Murrey (17) ]. Solid phosphorus trixode becomes luminescent [Thorpe and Tutton (29)]] and so do carbon monoxide, carbonyl sulfide, and carbonyl chloride at 200 C. The first of these furnishes a band spectrum of 4000 to 5000 A. which corresponds to a bimolecular process [Trautz and Seidel (31) and Trautz and Haller (30)]. Siloxane too shows oxyluminescence [Kautsky and Zocher (16)] under the influence of ozone. 

C.H. Hsueh, W.W. Wendlandt, Effect of some experimental parameters on the oxyluminescence curves of selected materials. Thermochim. Acta 99, 37-42 (1986)... 

W.W. Wendlandt, The oxyluminescence and kinetics of oxyluminescence of selected polymers. Thermochim. Acta 71, 129-137 (1983)... 

Degradation behaviour of polyamides continues to be the subject of many papers. The degradation of nylon-6 has been examined by hydrolysis,by photolysis, and ultrasonically. Kinetic studies on chain scission by means of e.s.r. spectroscopy showed that the concentration of free radicals originating from broken chains in nylon-6 fibres could be described by a model system in which crystalline and amorphous layers were sandwiched in the fibre direction. Oxyluminescence has also been used in a study of the kinetics of the thermo-oxidative degradation of nylon-6,6. 

Oxyluminescence (OL), i.e. weak visible chemiluminescence (CL) emitted during oxidation. 

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