Abstract
Layered double hydroxide (LDH) minerals are promising candidates for developing polymer nanocomposites and the exchange of intercalating anions and metal ions in the LDH structure considerably affects their ultimate properties. Despite the fact that the synthesis of various kinds of LDHs has been the subject of numerous studies, the cure kinetics of LDH-based thermoset polymer composites has rarely been investigated. Herein, binary and ternary structures, including [Mg0.75 Al0.25 (OH)2]0.25+ [(CO32−)0.25/2∙m H2O]0.25−, [Mg0.75 Al0.25 (OH)2]0.25+ [(NO3−)0.25∙m H2O]0.25− and [Mg0.64 Zn0.11 Al0.25 (OH)2]0.25+ [(CO32−)0.25/2∙m H2O]0.25−, have been incorporated into epoxy to study the cure kinetics of the resulting nanocomposites by differential scanning calorimetry (DSC). Both integral and differential isoconversional methods serve to study the non-isothermal curing reactions of epoxy nanocomposites. The effects of carbonate and nitrate ions as intercalating agents on the cure kinetics are also discussed. The activation energy of cure (Eα) was calculated based on the Friedman and Kissinger–Akahira–Sunose (KAS) methods for epoxy/LDH nanocomposites. The order of autocatalytic reaction (m) for the epoxy/Mg-Al-NO3 (0.30 and 0.254 calculated by the Friedman and KAS methods, respectively) was smaller than that of the neat epoxy, which suggested a shift of the curing mechanism from an autocatalytic to noncatalytic reaction. Moreover, a higher frequency factor for the aforementioned nanocomposite suggests that the incorporation of Mg-Al-NO3 in the epoxy composite improved the curability of the epoxy. The results elucidate that the intercalating anions and the metal constituent of LDH significantly govern the cure kinetics of epoxy by the participation of nitrate anions in the epoxide ring-opening reaction.
Highlights
Clay nanomaterials are the most well-known family of minerals in the field of nanoscience and nanotechnology [1]
Despite the fact that the synthesis of various kinds of Layered double hydroxide (LDH) has been the subject of numerous studies, the cure kinetics of LDH-based thermoset polymer composites has rarely been investigated
The results elucidate that the intercalating anions and the metal constituent of LDH significantly govern the cure kinetics of epoxy by the participation of nitrate anions in the epoxide ring-opening reaction
Summary
Clay nanomaterials are the most well-known family of minerals in the field of nanoscience and nanotechnology [1]. It is well known that the ultimate properties of thermoset reins are dependent on network formation during cure reactions [10,11,12]. The Cure Index (CI) was recently defined as a simple criterion to elucidate the curability of thermoset composites [22,23]. The use of the CI provided a rough image of the curability of the resulting nanocomposites, such that the enlargement of the gallery space of the LDH structure by anions supported network formation in the epoxy/LDH system. The effects of the Mg-Al-CO3, Mg-Al-NO3 and Mg-Zn-Al-CO3 LDH structure on curing kinetics of epoxy/amine systems were compared in terms of non-isothermal differential scanning calorimetry (DSC). Analyses were done using differential Friedman and integral Kissinger–Akahira–Sunose (KAS) isoconversional methods
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