Qualitative and quantitative evaluation of epoxy systems by Fourier transform infrared spectroscopy and the flexibilizing effect of mercaptans

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Abstract

Abstract Epoxy systems are widely applied as adhesives in the aerospace industry. They have excellent adhesion properties, however, being thermosetting, epoxy systems show fracture brittleness characteristics. Polysulfide and polymercaptans are good options to increase the flexibility of the epoxy adhesive. Thermal analysis techniques are generally used to evaluate the curing degree of epoxy systems. In most cases, when infrared (IR) analysis is used, it is employed qualitatively. This paper presents the reaction study of a DGEBA epoxy prepolymer with diethylenetriamine (DETA) and linear and branched dodecyl mercaptans as flexibilizers. Conversion data and curing time were assessed qualitatively and quantitatively by Fourier Transform Infrared Spectroscopy (FT-IR) in the medium infrared region (MIR) and in the near infrared region, using near infrared reflectance accessory (NIRA). NIRA methodology showed satisfactory results, with errors between 3 and 7%, especially in samples with lower amine contents. Mechanical tests confirmed the flexibilization of the cured epoxy system by the addition of mercaptans, indicating a lower crosslinking degree in the matrix. Young’s modulus (E) significantly decreased from 2017 MPa to 578 MPa with the addition of approximately 20 wt% of normal dodecyl mercaptan to the epoxy system.

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Mechanism of Yellowing: Carbonyl Formation during Hygrothermal Aging in a Common Amine Epoxy

Andrey E. Krauklis, Andreas Echtermeyer (2018)

Epoxies are often exposed to water due to rain and humid air environments. Epoxy yellows during its service time under these conditions, even when protected from UV radiation. The material’s color is not regained upon redrying, indicating irreversible aging mechanisms. Understanding what causes a discoloration is of importance for applications where the visual aspect of the material is significant. In this work, irreversible aging mechanisms and the cause of yellowing were identified. Experiments were performed using a combination of FT-NIR, ATR-FT-IR, EDX, HR-ICP-MS, pH measurements, optical microscopy, SEM, and DMTA. Such extensive material characterization and structured logic of investigation, provided the necessary evidence to investigate the long-term changes. No chain scission (hydrolysis or oxidation-induced) was present in the studied common DGEBA/HDDGE/IPDA/POPA epoxy, whilst it was found that thermo-oxidation and leaching occurred. Thermo-oxidation involved evolution of carbonyl groups in the polymeric carbon–carbon backbone, via nucleophilic radical attack and minor crosslinking of the HDDGE segments. Four probable reactive sites were identified, and respective reactions were proposed. Compounds involved in leaching were identified to be epichlorohydrin and inorganic impurities but were found to be unrelated to yellowing. Carbonyl formation in the epoxy backbone due to thermo-oxidation was the cause for the yellowing of the material.

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Analysis of the reaction mechanism of the thiol–epoxy addition initiated by nucleophilic tertiary amines

Ali Osman Konuray, Xavier Fernández-Francos, Xavier Ramis (2017)

The mechanism of thiol–epoxy reactions has been analyzed from a theoretical point of view and modelled using experimental kinetic data. A kinetic model for thiol–epoxy crosslinking initiated by tertiary amines has been proposed. The kinetic model is based on mechanistic considerations and it features the effect of the initiator, hydroxyl content, and thiol–epoxy ratios. The results of the kinetic model have been compared with data from the curing of off-stoichiometric formulations of diglycidyl ether of bisphenol A (DGEBA) crosslinked with trimethylolpropane tris(3-mercaptopropionate) (S3) using 1-methylimidazole (1MI) as the initiator. The model has been validated by fitting the kinetic parameters to the experimental data under a variety of reaction conditions. In spite of the experimental uncertainty and model assumptions, the main features of the curing kinetics are correctly described and the reaction rates are quantitatively reproduced.