Carbonyl Identification and Quantification Uncertainties for Oxidative Polymer Degradation

• Published in: Polymer degradation and stability Vol. 188; p. 109550
• Main Authors: Celina, Mathew C., Linde, Erik, Martinez, Estevan
• Format: Journal Article
• Language: English
• Published: London Elsevier Ltd 01.06.2021; Elsevier BV; Elsevier
• Subjects: absorbance; carbon; Carbon cycle; Carbonyl Quantification; Carbonyls; Coefficients; Degradation; Degradation Mechanisms; Infrared spectroscopy; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; IR Spectroscopy; Oxidation; Penetration depth; Polymer films; Polymer Oxidation; Polymers; refractive index; Refractivity; Studies; Uncertainty; Carbonyl Quantification; Polymer Oxidation; Degradation Mechanisms; IR Spectroscopy
• DOI: 10.1016/j.polymdegradstab.2021.109550
• ISSN: 0141-3910

•The use of IR spectroscopy as a key diagnostic for carbonyl formation is reviewed.•Carbonyl identification and quantification is challenging due to multiple uncertainties.•Significant range in peak position and extinction coefficients for carbonyl compounds.•Diverging data between transmission and different ATR IR approaches.•Existing data are often limited and not fully traceable. The most revealing indicator for oxidative processes or state of degraded plastics is usually carbonyl formation, a key step in materials degradation as part of the carbon cycle for man-made materials. Hence, the identification and quantification of carbonyl species with infrared spectroscopy have been the method of choice for generations, thanks to their strong absorbance and being an essential intermediate in carbon oxidation pathways. Despite their importance, precise identification and quantification can be challenging and rigorous fully traceable data are surprisingly rare in the existing literature. An overview of the complexity of carbonyl quantification is presented by the screening of reference compounds in solution with transmission and polymer films with ATR IR spectroscopy, and systematic data analyses. Significant variances in existing data and their past use have been recognized. Guidance is offered how better measurements and data reporting could be accomplished. Experimental variances depend on the combination of uncertainty in exact carbonyl species, extinction coefficient, contributions from neighboring convoluting peaks, matrix interaction phenomena and instrumental variations in primary IR spectral acquisition (refractive index and penetration depth for ATR measurements). In addition, diverging sources for relevant extinction coefficients may exist, based on original spectral acquisition. For common polymer degradation challenges, a relative comparison of carbonyl yields for a material is easily accessible, but quantification for other purposes, such as degradation rates and spatially dependent interpretation, requires thorough experimental validation. All variables highlighted in this overview demonstrate the significant error margins in carbonyl quantification, with exact carbonyl species and extinction coefficients already being major contributors on their own. [Display omitted]