The use of ionizing radiation offers a boundless range of applications for polymer scientists, from inducing crosslinking and/or degradation to grafting a wide variety of monomers onto polymeric chains. This review in particular aims to introduce the field of ionizing radiation as it relates to the degradation and recycling of cellulose and its derivatives. The review discusses the main mechanisms of the radiolytic sessions of the cellulose molecules in the presence and absence of water. During the radiolysis of cellulose, in the absence of water, the primary and secondary electrons from the electron beam, and the photoelectric, Compton effect electrons from gamma radiolysis attack the glycosidic bonds (C-O-C) on the backbone of the cellulose chains. This radiation-induced session results in the formation of alkoxyl radicals and C-centered radicals. In the presence of water, the radiolytically produced hydroxyl radicals (●OH) will abstract hydrogen atoms, leading to the formation of C-centered radicals, which undergo various reactions leading to the backbone session of the cellulose. Based on the structures of the radiolytically produced free radicals in presence and absence of water, covalent grafting of vinyl monomers on the cellulose backbone is inconceivable.
24 July 2019 in Journal of Radioanalytical and Nuclear Chemistry
The electrochemical oxidation of bifenox acid was studied at a boron-doped diamond thin film by cyclic voltammetry and galvanostatic electrolysis. The course of the electrolysis was monitored by measurement of chemical oxygen demand (COD) and by gas chromatography/mass spectrometry (GC / MS) analysis. It was found that exhaustive electrolysis leads to degradation and, ultimately, to mineralization of the starting herbicide. The degradation intermediates were identified showing that the oxidation process begins with the fragmentation of the molecule followed by reactions involving the hydroxyl radical, which is generated by the discharge of water. The study of the effect of current density and concentration showed that the degradation efficiency increases with decreasing current densities and increasing concentrations. The whole results were interpreted in a mechanistic scheme involving two oxidation pathways, the first is a direct oxidation at the electrode and the second uses hydroxyl radical as mediator of the oxidation. Finally, a kinetic study based on spectrophotometric measurements showed that the degradation process is pseudo first order.
An efficient gamma radiolytic decomposition of one of the extensively used herbicides in the world quizalofo-p-ethyl (QPE) was explored under different experimental conditions. Aqueous solutions of QPE were irradiated by gamma rays emitted by a Cobalt 60 source. QPE aqueous solutions were irradiated at doses of 0.5–3 kGy with 26.31 Gy min−1 dose rate. Obtained results indicated that removal efficiency of 98.5% and 73% of QPE were obtained, respectively, in absence and in presence of dissolved oxygen. Change of absorption spectra, pH effect and Total Organic Carbon (TOC) were carried out and studied. It was found that all absorption bands decreased with increasing irradiation dose and disappear totally after 3 kGy applied dose. Three pH conditions (pH = 10, pH = 6.2 and pH = 3) were applied in radiolytic degradation of QPE showing that the best removal efficiency has been found for neutral pH. Interestingly, the % TOC removal reaches 98% at 3 kGy indicated practically total mineralization. Furthermore, spectrophotometric analyses argued in favour of a pseudo-first-order kinetic of QPE degradation. The resulting apparent rate constant value is approximately kapp = (0.012 ± 0.001) min−1. Finally, several by-products such as 6-chloroquinoxalin -2-ol, 2-(4-hydroxy-phenyoxy) propionate, 1,4-hydroquinone, quinone, 4-chlorobenzene-1,2diol and 1,2,4-benzenetriol were identified by gas chromatography–mass spectrometry (GC/MS) evidencing that radiation process starting with the fragmentation of the molecule involving the hydroxyl radical, which is generated by the radiolysis of water. Based on the identification intermediates, a degradation mechanistic schema of QPE has been proposed. GRAPHICAL ABSTRACT