Curing Behavior and Thermomechanical Performance of Bioepoxy Resin Synthesized from Vanillyl Alcohol: Effects of the Curing Agent

In order to reduce the dependency of resin synthesis on petroleum resources, vanillyl alcohol which is a renewable material that can be produced from lignin has been used to synthesize bioepoxy resin. Although it has been widely reported that the curing reaction and properties of the cured epoxies can be greatly affected by the molecular structure of the curing agents, the exact influence remains unknown for bioepoxies. In this study, four aliphatic amines with different molecular structures and amine functionalities, namely triethylenetetramine (TETA), Tris(2-aminoethyl)amine (TREN), diethylenetriamine (DETA), and ethylenediamine (EDA), were used to cure the synthesized vanillyl alcohol–based bioepoxy resin (VE). The curing reaction of VE and the physicochemical properties, especially the thermomechanical performance of the cured bioepoxies with different amine functionalities, were systematically investigated and compared using different characterization methods, such as DSC, ATR–FTIR, TGA, DMA, and tensile testing, etc. Despite a higher curing temperature needed in the VE–TETA resin system, the cured VE–TETA epoxy showed a better chemical resistance, particularly acidic resistance, as well as a lower swelling ratio than the others. The higher thermal decomposition temperature, storage modulus, and relaxation temperature of VE–TETA epoxy indicated its superior thermal stability and thermomechanical properties. Moreover, the tensile strength of VE cured by TETA was 1.4~2.6 times higher than those of other curing systems. In conclusion, TETA was shown to be the optimum epoxy curing agent for vanillyl alcohol–based bioepoxy resin.

Thermal Properties of Plasticized Cellulose Acetate and Its β-Relaxation Phenomenon

Cellulose acetate (CA), an organic ester, is a biobased polymer which exhibits good mechanical properties (e.g., high Young’s modulus and tensile strength). In recent decades, there has been significant work done to verify the thermal and thermomechanical behaviors of raw and plasticized cellulose acetate. In this study, the thermomechanical properties of plasticized cellulose acetate—especially its ββ-relaxation and activation energy—were investigated. The general thermal behavior was analyzed and compared with theoretical models. The study’s findings could be of special interest, due to the known ββ-relaxation dependency of some polymers regarding mechanical properties—which could also be the case for cellulose acetate. However, this would require further investigation. The concentration of the plasticizers—glycerol triacetate (GTA) and triethyl citrate (TEC)—used in CA ranged from 15 to 40 wt%. DMTA measurements at varying frequencies were performed, and the activation energies of each relaxation were assessed. Increasing plasticizer content first led to a shift in ββ-relaxation temperature to highervalues, then reached a maximum before declining again at higher concentrations. Furthermore, the activation energy of the ββ-relaxation constantly rose with increases in plasticizer content. The trend in the ββ-relaxation temperature of the plasticized CA could be interpreted as a change in the predominant phase of the overlapping ββ-relaxation of the CA itself and the αα′-relaxation of the plasticizer—which appears in the same temperature range. The plasticizer used (GTA) demonstrated a higher plasticization efficiency than TEC. The efficiencies of both plasticizers declined with increasing plasticizer content. Additionally, both plasticizers hit the saturation point (in CA) at the lowest studied concentration (15 wt%).

Thermal Investigations on Carbon Nanotubes by Spectroscopic Techniques

Carbon nanotubes (CNTs) thanks to their unique physical properties have been employed in several innovative applications particularly for energy storage applications. Certain technical features of carbon nanotubes, such as their remarkable specific surface, mechanical strength, as well as their electron and thermal conductivity are suitable for these applications. Furthermore, in order to produce a device, thermal treatment is needed and for this reason the trend of thermal decomposition of the tubes plays a key role in the integration process. The main purpose of this work was to characterize the thermal behavior of CNTs. In particular, we show the findings of an experimental study on CNTs performed by means of Fourier Transform InfraRed and Raman spectroscopy investigations. The collected FTIR and Raman spectra were analyzed by using two innovative procedures: spectral distance (SD) and wavelet cross correlation (XWT). From both analyses, a relaxation temperature value emerged of T = 206 °C, corresponding to a relaxation inflection point. Such a system relaxation phenomenon, occurring in the fiber CNTs, could be connected with the decay of the mechanical properties due to a decrease in the alignment and compaction of the fibers.

In situ investigations of the phase change behaviour of tungsten oxide nanostructures

This study uses two in situ techniques to investigate the geometry and phase change behaviour of bundled ultrathin W 18 O 49 nanowires and WO 3 nanoparticles. The in situ X-ray diffraction (XRD) results have shown that the phase transition of WO 3 nanoparticles occurs in sequence from monoclinic (room temperature) → orthorhombic (350°C) → tetragonal (800°C), akin to bulk WO 3 ; however, W 18 O 49 nanowires remain stable as the monoclinic phase up to 500°C, after which a complete oxidation to WO 3 and transformation to the orthorhombic β-phase at 550°C is observed. The in situ Raman spectroscopy investigations have revealed the Raman peak downshifts as the temperature increases, and have identified the 187.6 cm −1 as the fingerprint band for the phase transition from γ- to β-phase of the WO 3 nanoparticle. Furthermore, WO 3 nanoparticles exhibit the γ- to β-phase conversion at 275°C, which is about 75°C lower than the relaxation temperature of 350°C for the monoclinic γ-W 18 O 49 nanowires. These new fundamental understandings on the phase transition behaviour offer important guidance for the design and development of tungsten oxide-based nanodevices by defining their allowed operating conditions.

Modeling and experimentation of multi-layered nanostructured graphene-epoxy nanocomposites for enhanced thermal and mechanical properties

The influence of multi-layered nanostructured graphene as reinforcement on thermal and mechanical properties of epoxy-based nanocomposites has been studied. The maximum improvement in mechanical properties was observed at 0.1 wt%. The Young’s and flexural moduli increased from 610 MPa to 766 MPa (26% increase) and 598.3 MPa to 732.8 MPa (23% increase), respectively. The tensile and flexural strengths increased from 46 MPa to 65 MPa (43% increase) and 74 MPa to 111 MPa (49% increase), respectively. The mode-1 fracture toughness (K1C) and critical strain energy release rate (G1C) increased from 0.85 MPa.m1/2 to 1.2 MPa.m1/2 (41% increase) and from 631 J/m2 to 685 J/m2 (9% increase), respectively. The increase in fracture toughness is attributed to the obstruction of cracks by graphene layers. The reinforcing effect of nanostructured graphene was also manifested in dynamic mechanical properties. The storage modulus and alpha-relaxation temperature values significantly increased indicating the fine integration of NSG in epoxy chains. The thermal properties of nanocomposites were simulated which showed that graphene is very efficient in significantly increasing the scattering and dissipation of thermal flux.