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Considering its great industrial potential, epoxidized linseed oil (ELO) was crosslinked with different agents, both natural and synthetic: citric acid (CA, in the presence of water—W, or tetrahydrofuran—THF, as activator molecules) and Jeffamine D230, respectively, resulting bio-based polymeric matrices, studied further, comparatively, in terms of their properties, through different methods. Thermal curing parameters were established by means of Differential Scanning Calorimetry (DSC). Fourier transform Infrared Spectroscopy (FTIR) and DSC were used to identify the reactivity of each ELO-based formulation, discussing the influence of the employed curing systems under the conversion of the epoxy rings. Then, the obtained bio-based materials were characterized by different methods, establishing the structure–properties relation. Thermogravimetric analysis revealed higher thermal stability for the ELO_CA material when THF was used as an activator. Moreover, a higher glass transition temperature (Tg) with ~12 °C was registered for this material when compared with the one that resulted through the crosslinking of ELO with D230 conventional amine. Other important features, such as crosslink density, storage modulus, mechanical features, and water affinity, were discussed. Under the loop of a comprehensive approach, a set of remarkable properties were obtained for ELO_CA_THF material when compared with the one resulting from the crosslinking of ELO with the synthetic Jeffamine.

To answer the question “How does lanthanide doping in iron oxide affect cure kinetics of epoxy-based nanocomposites?”, we synthesized samarium (Sm)-doped Fe3O4 nanoparticles electrochemically and characterized it using Fourier-transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive X-Ray analysis (EDX), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy analyses (XPS). The magnetic particles were uniformly dispersed in epoxy resin to increase the curability of the epoxy/amine system. The effect of the lanthanide dopant on the curing reaction of epoxy with amine was explored by analyzing differential scanning calorimetry (DSC) experimental data based on a model-free methodology. It was found that Sm3+ in the structure of Fe3O4 crystal participates in cross-linking epoxy by catalyzing the reaction between epoxide rings and amine groups of curing agents. In addition, the etherification reaction of active OH groups on the surface of nanoparticles reacts with epoxy rings, which prolong the reaction time at the late stage of reaction where diffusion is the dominant mechanism.

Here, we propose a novel attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy method for simultaneously monitoring the curing reaction and the diffusion behavior of curing agents at the surface of rubber in real-time. The proposed scheme was demonstrated by fluorine rubber (FKM) and FKM/carbon nanotube (CNT) nanocomposites with a target curing agent of triallyl-isocyanurate (TAIC). The broadening and the evolution of the C=O stretching of TAIC were quantitatively analyzed to characterize the reaction and the diffusion. Changes in the width of the C=O stretching indicated the reaction rate at the surface was even faster than that of the bulk as measured by a curemeter. The diffusion coefficient of the curing agent in the course of heating was newly calculated by the initial increase in the absorbance and our model based on Fickian diffusion. The diffusion coefficients of TAIC during curing were evaluated, and its temperature and filler dependency were identified. Cross-sectional ATR-FTIR imaging and in situ ATR-FTIR imaging measurements supported the hypothesis of the unidirectional diffusion of the curing agent towards the heated surface. It was shown that our method of in situ ATR-FTIR can monitor the degrees of cure and the diffusion coefficients of curing agents simultaneously, which cannot be achieved by conventional methods, e.g., rheological measurements.

Unsaturated polyester resin (UP) is a critical polymer material in applications of many fields, such as the chemical industry, military, and architecture. For improving the mechanical properties, some hardeners, such as methyl ethyl ketone peroxide (MEKPO) or tert-butyl peroxy-2-ethylhexanoate (TBPO), can trigger the curing reaction in UP polymerization, which causes that UP changes the structure from monomer to polymer. However, polymerization is a strong exothermic reaction, which can increase the risk of thermal runaway reaction in UP. Therefore, the mechanisms and characteristics in the thermal runaway reaction of UP mixed with hardeners should be studied for preventing and controlling UP explosion. The thermal hazards of UP mixed with hardeners were determined by thermogravimetric analyzer (TGA) and differential scanning calorimetry (DSC) analysis. According to the results, UP mixed with MEKPO exhibited a more violent mass loss and exothermic reaction than UP mixed with TBPO. Furthermore, the thermal runaway reactions of UP mixed with MEKPO or TBPO with different mixing proportions of 1:1, 3:1, and 5:1 were determined. Irrespective of MEKPO or TBPO, the mixing proportions of 3:1 exhibited a high onset temperature and low enthalpy of curing reaction (ΔHexo). This demonstrated that this proportion was safer during UP polymerization. The results of this study can provide useful information for preventing UP explosion and developing polymerization technology.

Recent experimental results showed that the Tg of cured resin scarcely decreased and the impact strength of resins increased by over 50% when a tetrafunctional epoxy named N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl ether (TGDDE) was introduced to an appropriate flexible chain from a dimer fatty acid (DFA). In order to understand the reason for this phenomenon, the modification and the chemical structure of the prepolymer together with the curing reaction and the viscoelasticity of the cured resins were studied in detail in the present work. The results indicated that the modification would help the prepolymer improve its molecular mobility. As a result, the resins could be further cured, resulting in the cross-linking density increasing. This is because the curing efficiency was increased, but the tetrafunctional epoxy was not cured completely due to its large steric hindrance. Moreover, the flexibility of some parts of the networks was improved, which was beneficial for the toughness of the cured resins. Therefore, the toughness of the tetrafunctional resin was improved with little influence on the thermal properties when the epoxies were modified with an appropriate content of DFA.

Self-healing cementitious composites have been developed by using microcapsules. In this study, the effect of the healing agent on the crosslinking and curing reaction kinetics was analyzed. The effect of the diluent n-butyl glycidyl ether (BGE) on the reaction was investigated for five fractions, namely 10.0%, 12.5%, 15.0%, 17.5%, and 20.0% mass fractions to epoxy resin. The Kissinger and Crane equations were used to obtain the activation energy and reaction order with different mass fractions of diluent, as well as the kinetic parameters of the curing reaction. The optimal fraction of BGE was determined as 17.5%. Likewise, the effect of the curing agent MC120D on the reaction kinetics was investigated for 10%, 20%, 30%, 40%, and 50% mass fractions to the diluted epoxy resin. The optimal fraction was determined as 20%. The mechanism of the curing reaction with the healing agent was investigated. The infrared spectra of the cured products of 20% MC120D with BGE/E51 (0.0%, 12.5%, 15.0%, 20.0%, 100%) were analyzed. It is shown that not only the epoxy resin E-51 was cured, but also that the BGE was involved in the cross-linking reaction of the epoxy resin E-51 with MC120D.