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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]

Coffee is one of the most popular beverages in the world but generates copious amounts of waste that is usually discarded. This discarded waste, the so‐called spent coffee grounds (SCGs), can become a valuable resource if compelling use cases are found. Following a circular economy approach, one such use case can be employing SCGs as filler in polymer matrices, complementing conventional inorganic fillers such as kaolin clay. This work studies the effect of SCGs as filler in wholly natural thermosets, investigating changes in curing kinetics and final material properties. Different SCG content, for example, 25 to 35 wt% and various curing time and temperature is employed. SCGs are found to have a moderate catalytic effect on the curing reaction. Furthermore, SCGs are found to heavily increase stiffness of the final material, especially when oils present in SCGs are previously extracted, raising the rubber plateau modulus from around 5 MPa to 14 MPa. Extracted SCGs are most efficient during curing at room temperature, where they significantly improved the tensile strength, toughness, and hardness of the filled material compared to the pristine resin. [ABSTRACT FROM AUTHOR]

Abstract: The biaxial orientation behavior of poly(ethylene 2,5‐furandicarboxylate) (PEF) is studied in comparison to poly(ethylene terephthalate) (PET). PEF is a polyester that can be produced through similar steps as PET but using 100% biobased 2,5‐furandicarboxylic acid instead of terephthalic acid. This work highlights the stress–strain behavior of PEF during biaxial orientation at various temperatures. Strain hardening and strain‐induced crystallization in the oriented PEF samples generally appeared at higher stretch ratios for PEF than for PET at comparable molecular weight, while somewhat lower degrees of crystallinity are reached in PEF. Shrinkage in oriented PEF is found to be on par with PET in the region of the glass transition. Higher modulus and improved barrier properties, compared to PET, are found in the oriented materials when sufficiently high stretch ratios are applied in biaxial orientation. [ABSTRACT FROM AUTHOR]

The effect of nanocrystalline cellulose dispersion on the nonisothermal crystallization of poly(ethylene 2,5-furandicarboxylate) (PEF) has been investigated by means of solvent casting. The cellulose dispersion plays a significant role on the crystallization temperature, thus dispersive equipments of increasing energies were employed to improve the cellulose particles disaggregation. Therefore, ultra-sonic bath, ultra-sonication, and ultra-turrax were used to disperse cellulose nanocrystals in 1,1,1,3,3,3-hexafluoro-2-propanol. Dissolved separately in the same solvent, PEF was then poured into the cellulose suspension before casting. The cellulose whiskers were inspected by transmission electron microscopy. Differential scanning calorimetry was used to measure the crystallization temperature, while scanning electron microscopy visualized the cellulose dispersion at the fracture surface. After investigation on the interaction of cellulose/PEF via Fourier transform infrared spectroscopy, the thermal stability of the blends was measured by means of thermogravimetric analysis. [ABSTRACT FROM AUTHOR]

Following the previous work (Phys. Chem. Chem. Phys., 2016, 18, 32021), this study continues to investigate the intriguing phenomenon of thermal decomposition during continuous cooling. The phenomenon can be detected and its kinetics can be measured by means of thermogravimetric analysis (TGA). The kinetics of the thermal decomposition of ammonium nitrate (NH4NO3), nickel oxalate (NiC2O4), and lithium sulfate monohydrate (Li2SO4·H2O) have been measured upon heating and cooling and analyzed by means of the isoconversional methodology. The results have confirmed the hypothesis that the respective kinetics should be similar for single-step processes (NH4NO3 decomposition) but different for multi-step ones (NiC2O4 decomposition and Li2SO4·H2O dehydration). It has been discovered that the differences in the kinetics can be either quantitative or qualitative. Physical insights into the nature of the differences have been proposed. [ABSTRACT FROM AUTHOR]

The glass transition of poly(ethylene 2,5-furandicarboxylate) (PEF), an emergent bio-based polyester, was investigated in comparison to one of its chemical analogues: poly(ethylene terephthalate) (PET). These investigations were conducted at different crystallinities by means of stochastic modulated differential scanning calorimetry (stochastic TMDSC) and dynamic mechanical analysis (DMA). Amorphous PEF presents a higher ΔCp at the glass transition and a broader relaxation spectrum attributed to a higher free volume. The higher Tg of PEF is then purely related to segmental mobility and specific interactions in PEF. The length of cooperative rearranging regions (CRR) was similar for both materials. Additionally, the variations of the effective activation energy E of PEF and PET at glass transitions were determined by isoconversional kinetic analysis. The rate of decrease in E was similar for the two amorphous polyesters. Upon crystallization, the glass transition of PEF is broadened but its temperature range is not increased as with PET. The creation of the rigid amorphous fraction (RAF) with crystallinity is lower in PEF than in PET. The difference in free volume also explains the lower coupling between the crystalline phase and the amorphous phase in PEF. [ABSTRACT FROM AUTHOR]

The present work focuses on the influence of nucleation processes on the crystallization of bio-based poly(ethylene 2,5-furandicarboxylate) (PEF). Nuclei formation has been studied by means of fast scanning calorimetry (FSC) both when cooling from the melt (nonisothermal conditions) and when annealing at either low- or high-temperatures (isothermal conditions). FSC results show that nucleation on cooling can be prevented by using fast rates allowing to keep the polymer in its amorphous state; whereas cooling at moderate rates results in sample nucleation with a subsequent increase of the crystallization rate. Isothermal pretreatment just above the PEF glass transition temperature ( Tg) results in nuclei formation whose rate decreases when the nucleation temperature approaches PEF Tg. On the other hand, annealing below the PEF melting point allows determination of the sample self-nucleation behavior which occurs in a very narrow temperature range, i.e., between 195 and 198 °C. [ABSTRACT FROM AUTHOR]

Epoxidized linseed oil and furfuryl alcohol are bio-sourced monomers known for their high-potential applications in materials science. In this work, we propose the association of these monomers through copolymerization reactions with the target to design fully bio-based thermosets. Herein, investigations on cationic polymerization reactivity have been explored using differential scanning calorimetry. The obtained structures have been confirmed by IR spectroscopy and 2D NMR spectroscopy, which revealed the principal chain connections. In spite of the multiple capabilities of chemical connections, which include copolymerization and cross-linking, the obtained networks are homogeneous as confirmed by dynamic mechanical analysis and SEM. Furthermore, the copolymer demonstrates a semiductile behavior if subjected to tensile measurements (tensile strain at break.≈40%), which is a significant advance in terms of its applications as a furanic bio-based thermoset material. [ABSTRACT FROM AUTHOR]

Poly(ethylene 2,5-furandicarboxylate) (PEF) is a polyester from ethylene glycol and 2,5-Furandicarboxylic acid which has gained increasing interest due to its excellent properties compared to chemically similar PET. This paper presents an estimation of the crystallization enthalpy, the crystalline and amorphous density and the crystallization kinetics of PEF. Using Avrami and the Hoffman-Lauritzen theory, Hoffman-Lauritzen parameters are proposed that relate crystal growth rate of catalyst-free PEF to temperature and molecular weight. Characteristic is a higher activation energy for chain diffusion (U*) for PEF compared PET, which can be attributed to more restricted chain conformational changes. Finally, the crystallization rate of PEF is shown to be significantly affected by catalyst type. [ABSTRACT FROM AUTHOR]

Never-dried sulfite wood pulp was beaten and subsequently microfibrillated before being submitted to periodate oxidation for various times. The oxidation progress, which was followed by C solid-state NMR spectroscopy in conjunction with degree of oxidation (DO) measurements together with ultrastructural observations, revealed that the cellulose crystallinity and microfibrillar integrity were kept intact until a DO of 0.3/0.4, indicating that at that level, the cellulose microfibrils had been oxidized exclusively at their surface. Beyond this DO value, the sample crystallinity started to deteriorate, as the oxidation progressed toward the core of the microfibrils. Remarkably, throughout the oxidation, the created carbonyl moieties were never observed, as they were readily recombined into hemiacetals by cyclization either within the same anhydro glucose unit (AGU) or with the adjacent un-oxidized AGUs of the same cellulose chain. At DO below 0.3/0.4, hemiacetal coupling with adjacent cellulose chains was also considered, but it appeared unlikely in view of the interchain distance imposed by the crystalline lattice. The oxidized samples were subjected to a reductive amination with benzylamine in order to convert their hydrophilic surfaces into hydrophobic ones. Despite the ease of this derivatization, the analysis of the C solid-state NMR spectra of the aminated products showed that, below a DO of 0.3, only half of the hemiacetal moieties could be converted into secondary amine products, whereas the other half remained untouched, likely for steric reasons. [ABSTRACT FROM AUTHOR]

Silica nanoclusters were homogeneously dispersed into an end-linked PolyDiMethylSiloxane (PDMS) matrix. Dynamic relaxation, glass and melt crystallization of end-linked PDMS–silica nanocomposites (PDMSnanoSi) were compared to those of PDMS. A particular emphasis is made on the kinetic aspects of these transitions by corroborating investigations conducted by means of Dynamic Mechanical Analysis (DMA) and Differential Scanning Calorimetry (DSC). Addition of silica nanoclusters does not modify the relaxation behavior of the amorphous phase and the glass transition kinetics. However, melt and glass crystallizations are significantly promoted in the presence of silica nanoclusters. The secondary crystallization process is more pronounced for PDMSnanoSi and higher crystal perfection due to structuring effects of silica nanoclusters is also highlighted. For the two systems, one set of Hoffman–Lauritzen parameters have been evaluated by combining melt and glass crystallization kinetic data. [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]

Polytetrafluoroethylene (PTFE) is a polymer that displays exceptional properties. This synthetic fluoropolymer is also known to crystallize very fast upon cooling. The present work highlights for the first time the influence of nanosilica clusters on PTFE crystallization at fast cooling rates (up to 5000 K·s−1). The silica was synthesized from aqueous silicate solution and the surface modification was performed using TriEthoxyFluoroSilane (TEFS). In order to understand the crystallization behavior of PTFE/silica nanocomposite at a fast cooling rate, the measurements were carried out by Fast Scanning Calorimetry (FSC). The data were consequently combined with the measurements performed by conventional Differential Scanning Calorimetry (DSC). Interestingly, the results displayed variation of the crystallization behavior for the nanocomposite at fast cooling rates compared to slow cooling rates. The differences in crystal morphologies were then observed by Scanning Electron Microscopy (SEM) after slow and fast cooling rates. Finally, the effective activation energies (Eα) obtained from the crystallization under various cooling rates were combined in order to obtain one set of Hoffman-Lauritzen parameters. This procedure allowed us to show that the crystallization of PTFE in the presence of silica is promoted or hampered according to the cooling rates employed. [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]