The complete curing of furfuryl alcohol (FA), was studied by chemorheological analysis and model-free kinetics under isothermal and non-isothermal modes. Polymerization of FA under acidic catalysis involves complex reactions, with several steps (such as condensations and Diels-Alder cycloadditions). To account for the polymerization complexity, kinetic analysis of DSC data was performed with a model-free isoconversional method. The obtained E(alpha)-dependencies were closely-correlated with the variation of complex viscosity during curing. Linear condensations are predominant during the early curing stage and are followed by two distinct stages of branching cycloadditions. Gelation and vitrification, identified by rheometric measurements, were associated with a decrease of the overall reaction rate that becomes controlled by diffusion of small oligomers. Before vitrification, the rate of crosslinking is limited by the mobility of longer polymer chains and diffusion encounters a large energy barrier due to the cooperative nature of the motions, leading to higher E(alpha) values.
A challenge
of today’s industry is to transform low-value
side products into more value-added materials. Humins, a byproduct
derived from sugar conversion processes, can be transformed into high
value-added products. Thermosetting furanic composites were elaborated
with cellulose filters. Large quantities of humins were included into
a polyfuranic thermosetting network. Comparisons were made with composites
generated with polyfurfuryl alcohol (PFA) and with PFA/lignin. It
was concluded that new chemical interactions were created between
the side-chain oxygen groups of the humins and the PFA network. Analysis
of the fracture surface of the composites containing humins lead to
the conclusion that higher interfacial bonding and more efficient
stress transfer between the matrix and the fibers is present. The
higher ductility of the humins-based matrix allows for a two-fold
higher tensile strength in comparison with other composites tested.
Incorporation of humins decreases the brittleness of the furanic composites,
which is one major drawback of the pure PFA composites.
This work reports for the first time the copolymerization studies of 11 newly synthesized epoxidized vegetable oils (EVOs) that reacted with a disulfide-based aromatic dicarboxylic acid (DCA) to produce thermoset materials with recyclability properties. These new EVOs' reactivity and properties were compared with those of the two commercial references: epoxidized linseed oil (ELO) and epoxidized soybean oil (ESO). The structure−reactivity correlation is proposed by differential scanning calorimetry (DSC) analysis, corroborating the epoxy content of EVO monomers, the initiator effect, the copolymerization reaction enthalpy, and the temperature range. The thermomechanical properties of the obtained thermosets were evaluated and discussed in correlation with the structure and reactivity of monomers by dynamic mechanical analysis (DMA), tensile testing, and thermogravimetric analysis (TGA). It has been found that the higher the EVO functionality, the higher is the reactivity, cross-linking density, and final performances, with tan δ values ranging from 34 to 111 °C. This study investigates the chemical recycling and the solvent resistance of these vitrimerlike materials that have a high bio-based carbon content, from 58 to 79%, with potential application in coating or composite materials in the automotive sector.
Complex cure kinetics involved in the elaboration of organic/inorganic hybrid silicate nanocomposites based on diglycidyl ether of bisphenol A (DGEBA), 1,3-phenylenediamine (m-PDA), and modified montmorillonite (MMTm) clay have been studied. An advanced isoconversional method has been applied to nonisothermal data in order to evaluate cure kinetic parameters. A new method based on nonlinear optimization was proposed to compute nonisothermal kinetic parameters avoiding complex optimization techniques. The objective is to obtain kinetic parameters rather than modeling values in order to give more insight into the elucidation of complex cure mechanisms. Key kinetic parameters of cure have been computed according to this method. It appears that the reaction mechanism changes if MMTm is added to the curing system. The results reveal an increase of the efficiency of collisions in presence of MMTm at the beginning of the cure and an increase of the frequency of diffusion jumps at the later stage of the reaction.
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