Biobased poly(butylene 2,5-furandicarboxylate) and poly(butylene adipate-co-butylene 2,5-furandicarboxylate)s: From synthesis using highly purified 2,5-furandicarboxylic acid to thermo-mechanical properties

To synthesize high quality (co)polyesters derived from 2,5-furandicarboxylic acid (FA), an acetic acid refluxing/pH-swing method was proposed to purify FA. 2-Carboxyl furfural and other impurities were removed completely from FA with this method. Using highly purified FA, biobased polyester poly(butylene furnadicarboxylate) (PBF) and aliphatic-aromatic copolyesters poly(butylene adipate-co-butylene 2,5-furandicarboxy-late)s (PBAFs) were synthesized via melt (co)polycondensation. The (co)polyesters were characterized with GPC, FTIR, ¹H NMR, DSC and TGA, and their tensile mechanical properties were also assessed. The copolyesters possess random chain structure, monomer feed ratio-controlled copolymer composition and excellent thermal stability (T_d,5% > 340 °C) in full composition range. Both BA-rich and BF-rich PBAFs are crystalline polymers. The crystallizability decreases with composition, up to nearly amorphous at moderate ?_BF (40–60%). PBAFs with ?_BF no more than 50% exhibit obvious high-elastic deformation and rebound resilience, and possess tensile properties (E 18–160 MPa, σ_b 9–17 MPa, ε_b 370–910%) comparable to poly(butylene adipate). PBAFs with higher ?_BF behave like nonrigid plastics with low tensile moduli (42–110 MPa), moderate strength (30–42 MPa) and high elongation at break (310–470%). In comparison, PBF is a strong and tough thermoplastic having balanced mechanical properties, namely, much higher tensile modulus (1.9 GPa) and strength (56 MPa) and high elongation at break (260%). It seems necessary and effective to use highly purified FA for synthesizing high performance FA-derived (co)polyesters.     

Friction Properties of Fluorinated Graphitized Carbon Blacks

The tribologic properties of graphitized carbon blacks and their fluorinated derivatives are investigated as a function of the fluorination rate. Very low intrinsic friction coefficients are obtained for highly fluorinated compounds. The correlation of the tribologic results and structural investigations of the initial compounds by TEM strongly suggests that the friction mechanisms involve surface effects in the early stage of friction. Long-term tribologic experiments and Raman analyses point out an evolution of the structure and composition of the tribofilms during the friction process leading to similar friction properties of the tribofilms. Wear studies revealed that highly fluorinated derivatives appear less efficient than pristine and weakly fluorinated compounds.     

Arylene bisimides with triarylamine N-substituents as new solution processable organic semiconductors: Synthesis,spectroscopic, electrochemical and electronic properties

New solution processable organic semiconductors, consisting of pyrromelitic, naphthalene or perylene bisimide core and triarylamine N-substituents, have been synthesized. All three compounds are electrochemically active and undergo quasi-reversible oxidation and reduction as evidenced by cyclic voltammetry investigations. The oxidation process involves the transformation of the triarylamine substituents into radical cations as proven spectroscopically and spectroelectrochemically. The reduction process occurs at the arylene bisimide core leading to the formation of a radical anion and eventually a dianion in the second step. These findings are in perfect agreement with the DFT calculations which show that in the synthesized molecules the HOMO orbital is located on the triarylamine moiety whereas the LUMO one on the bisimide core. In all molecules studied the electrochemically determined ionization potential (IP) is slightly higher than 5.0 eV whereas in naphthalene and perylene derivatives the electron affinity (EA) is close to ?3.9 eV. These values fulfill the requirements for n-type (electron) semiconductors in air operating n-channel field effect transistors (FETs) as well as for p-type (hole) conductors in p-channel FETs. To verify whether the newly synthesized compounds exhibit the expected electrical transport properties all organic (CYTOP dielectric) test transistors were fabricated. All three semiconductors showed no field effect in the n-channel configuration. To the contrary, they could be used in p-channel FETs showing, in the saturation regime, the hole mobility approaching 10^?4 cm² V^?1 s^?1 – the value which slightly exceeds that measured for low molecular weight, amorphous triarylamine semiconductors.     

Friction Properties of Fluorinated Carbon Nanodiscs and Nanocones

The tribologic properties of carbon nanodiscs and nanocones and their fluorinated derivatives are investigated and correlated to their structure and chemical composition (atomic fluorine/carbon ratio). Two families of products are studied obtained by fluorination of ill ordered and highly graphitized carbon nanodiscs and nanocones. The studies clearly point out that friction properties of the nanoparticles are strongly dependent on the structure of the initial carbonaceous compounds. Better tribologic behaviour is obtained when the initial nanoparticles structure is highly ordered (graphitized particles). In that case, an optimum of fluorination rate is put in evidence.     

Trajectory Analysis of Forest Cover Change in the Tropical Dry Forest of Burkina Faso,West Africa

Forest cover decline is one of the most important environmental issues in the tropics. The present study was carried out in Burkina Faso, West Africa, and aimed at assessing the trajectories of forest cover change and measuring landscape metrics of the trajectory classes in order to better understand the processes of change. Landsat and ASTER images acquired over a period of 30 years were used for cover change detection and the Fragstats package was used to compute landscape metrics with five unifying change classes. Results showed a substantial increase in cropland with concurrent decline in forest cover. Deforestation represented 63% of the Percentage of Landscape (PLAND) in 2006, while reforestation accounted for only 28%. Both of these classes had high Normalized Landscape Shape Index (NLSI) values, indicating that they were present as scattered small patches. The old cultivation (30-year permanent cropland) was aggregated (IJI ≈ 0) while deforestation exhibited highly interspersed patches. The old forest and old cultivation presented lower Area Weighted Fractal Dimension Index (FRAC_AM), but deforestation and reforestation had the higher FRAC_AM. These results confirmed that there was a high level of deforestation and fragmentation in southern Burkina Faso and justify the need for a proper management plan to ensure the sustainable use of forest resources.     

High‐Temperature Neutron Diffraction,Raman Spectroscopy,and First‐Principles Calculations of Ti3SnC2 and Ti2SnC

Herein, we report—for the first time—on the additive‐free bulk synthesis of Ti₃SnC₂. A detailed experimental study of the structure of the latter together with a secondary phase, Ti₂SnC, is presented through the use of X‐ray diffraction (XRD), and high‐resolution transmission microscopy (HRTEM). A previous sample of Ti₃SnC₂, made using Fe as an additive and Ti₂SnC as a secondary phase, was studied by high‐temperature neutron diffraction (HTND) and XRD. The room‐temperature crystallographic parameters of the two MAX phases in the two samples are quite similar. Based on Rietveld analysis of the HTND data, the average linear thermal expansion coefficients of Ti₃SnC₂ in the a and c directions were found to be 8.5 (2)·10^?6 K^?1 and 8.9 (1)·10^?6 K^?1, respectively. The respective values for the Ti₂SnC phase are 10.1 (3)·10^?6 K^?1 and 10.8 (6)·10^?6 K^?1. Unlike other MAX phases, the atomic displacement parameters of the Sn atoms in Ti₃SnC₂ are comparable to those of the Ti and C atoms. When the predictions of the atomic displacement parameters obtained from density functional theory are compared to the experimental results, good quantitative agreement is found for the Sn atoms. In the case of the Ti and C atoms, the agreement is more qualitative. We also used first principles to calculate the elastic properties of both Ti₂SnC and Ti₃SnC₂ and their Raman active modes. The latter are compared to experiment and the agreement was found to be good.     

Design of New Cardanol Derivative: Synthesis and Application as Potential Biobased Plasticizer for Poly(lactide)

A novel biobased plasticizer made of cardanol is designed for poly(lactide) (PLA). This cardanol‐derived plasticizer, i.e., methoxylated hydroxyethyl cardanol (MeCard), is synthesized through methoxylation of the double bonds on the side chain of cardanol, and characterized by ¹H NMR and mass spectrometry. The plasticization effect of MeCard on the molecular structure, morphology, thermal and mechanical properties of PLA is evaluated and compared to that of a commercial cardanol, i.e., hydroxyethyl cardanol (pCard). The plasticization efficiency of MeCard is demonstrated by a substantial decrease of the glass transition temperature and storage modulus together with a significant increase of the elongation at break as compared to neat PLA. Moreover, MeCard exhibits higher plasticization performance than pCard toward PLA. Such behavior is related to a higher miscibility and compatibility between PLA and MeCard thanks to the methoxylation of the double bonds on the side chain of cardanol as shown by SEM micrographs.