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The biaxial behavior of PEF has been analyzed for equilibrated and simultaneous biaxial stretching. The ability of PEF to develop an organized microstructure through strain induced crystallization (SIC) has been described. Upon biaxial stretching, SIC can be difficult to perform because the stretching is performed in two perpendicular directions. However, thanks to the time/temperature superposition principle and an accurate heating protocol, relevant stretching settings have been chosen to stretch the material in its rubbery-like state and to reach high levels of deformation. By the protocol applied, the mechanical behavior is easily transposable to the industry. This work has shown that PEF can, as in uniaxial stretching, develop well-organized crystals and a defined microstructure upon biaxial stretching. This microstructure allows the obtention of improved mechanical properties and thermal stability of the biaxially stretched samples. The crystals induced upon biaxial stretching are similar to the one that has been developed and observed after uniaxial stretching and upon static crystallization. Moreover, the furan cycles seem to appear in a state similar to the one of a sample crystallized upon quiescent condition. The rigidity is increased, and the α-relaxation temperature is increased by 15 °C. [ABSTRACT FROM AUTHOR]

Humins is a biomass-derived material, co-product of the acid-catalyzed conversion of cellulose and hemicellulose to platform chemicals. This work presents a thorough study concerning the crosslinking kinetics of humins by chemorheological analysis and model-free kinetics under isothermal and non-isothermal curing. Humins can auto-crosslink under the effect of temperature, and the reaction can be fastener when adding an acidic initiator. Thus, the effect of P-Toluenesulfonic acid monohydrate (pTSA) on the crosslinking kinetics was also studied. The dependencies of the effective activation energy (Eα-dependencies) were determined by an advanced isoconversional method and correlated with the variation of complex viscosity during curing. It is shown that humins curing involves multi-step complex reactions and that the use of an acidic initiator allows faster crosslinking at lower temperatures, involving lower Eα. The shift from chemical to diffusion control was also estimated. [ABSTRACT FROM AUTHOR]

Furfuryl alcohol (FA) is a biobased monomer derived from lignocellulosic biomass. The present work describes its polymerization in the presence of protic polar solvents, i.e., water or isopropyl alcohol (IPA), using maleic anhydride (MA) as an acidic initiator. The polymerization was followed from the liquid to the rubbery state by combining DSC and DMA data. In the liquid state, IPA disrupts the expected reactions during the FA polymerization due to a stabilization of the furfuryl carbenium center. This causes the initiation of the polymerization at a higher temperature, which is also reflected by a higher activation energy. In the water system, the MA opening allows the reaction to start at a lower temperature. A higher pre-exponential factor value is obtained in that case. The DMA study of the final branching reaction occurring in the rubbery state has highlighted a continuous increase of elastic modulus until 290 °C. This increasing tendency of modulus was exploited to obtain activation energy dependences (Eα) of FA polymerization in the rubbery state. [ABSTRACT FROM AUTHOR]