Mechanochemical and thermal succinylation of softwood sawdust in presence of deep eutectic solvent to produce lignin-containing wood nanofibers

In this study, the effect of the deep eutectic solvent (DES) based on triethylmethylammonium chloride and imidazole on the mechanochemical succinylation of sawdust was investigated. The sawdust was ball milled in the presence of succinic anhydride and the effects of different amounts of the DES on the carboxylic acid content and particle size were studied with and without post-heating. The carboxylic acid content significantly increased with the addition of the DES and by using 1.5 mass excess of the DES compared to sawdust; milled sawdust with 3.5 mmol/g of carboxylic acid groups was obtained using 60 min post-heating at 100 °C. The particle size was found to depend strongly on DES-to-wood ratio and a change in size-reduction characteristics was observed related to fiber saturation point. After mechanochemical milling, three succinylated sawdust samples with different carboxylic acid contents were disintegrated into wood nanofibers and self-standing films were produced. Although the mechanical properties of the films were lower than the cellulose nanofibers, they were higher or in line with oil- and biobased polymers such as polypropene and polylactic acid, respectively. Because of their amphiphilic nature, wood nanofibers were found to be effective stabilizers of water–oil emulsions.

Transport and Dielectric Properties of Mechanosynthesized La2/3Cu3Ti4O12 Ceramics

La2/3Cu3Ti4O12 (LCTO) powder has been synthesized by the mechanochemical milling technique. The pelletized powder was conventionally sintered for 10 h at a temperature range of 975–1025 °C, which is a lower temperature process compared to the standard solid-state reaction. X-ray diffraction analysis revealed a cubic phase for the current LCTO ceramics. The grain size of the sintered ceramics was found to increase from 1.5 ± 0.5 to 2.3 ± 0.5 μm with an increase in sintering temperature from 975 to 1025 °C. The impedance results show that the grain conductivity is more than three orders of magnitude larger than the grain boundary conductivity for LCTO ceramics. All the samples showed a giant dielectric constant (1.7 × 103–3.4 × 103) and dielectric loss (0.09–0.17) at 300 K and 10 kHz. The giant dielectric constant of the current samples was attributed to the effect of internal barrier layer capacitances due to their electrically inhomogeneous structure.

Investigations of Thermally-Controlled Mechanochemical Milling Reactions

Mechanochemical milling reactions gained a lot of attention lately as a green and highly efficient path towards various relevant materials. The control over the fundamental reaction parameters in milling procedure, such as temperature and pressure of the reactor, is still in infancy and the vast majority of milling reactions is done with controlling just the basic parameters such as frequency and milling media weight. We demonstrate here how the milling under controlled, prolonged and variable heating programs accomplished in a new milling reactor introduces a new level of mechanochemical reactivity beyond what can be achieved by conventional mechanochemical or solution procedures, and also reduces the time and energy costs of the milling process. The methodology is demonstrated on four varied systems: C–C bond forming Knoevenagel condensation, selective C–N bond formation for amide/urea synthesis, selective double-imine condensation, and solid-state formation of an archetypal open metal-organic framework, MOF-74. The potential of this methodology is best demonstrated on the one-pot selective synthesis of four complex products containing combinations of amide, amine or urea functionalities from the same and simple acyl azide and diamine reactants. Principal control over this enhanced reactivity and selectivity stemmed from the application of specific heating regimes to mechanochemical processing accomplished by a new, in-house developed mechanochemical reactor. As even the moderate increase in temperature strongly affects the selectivity and the rate of mechanochemical reactions, the results presented are in line with recent challenges of the accepted theories of mechanochemical reactivity.

Investigations of Thermally-Controlled Mechanochemical Milling Reactions

Mechanochemical milling reactions gained a lot of attention lately as a green and highly efficient path towards various relevant materials. The control over the fundamental reaction parameters in milling procedure, such as temperature and pressure of the reactor, is still in infancy and the vast majority of milling reactions is done with controlling just the basic parameters such as frequency and milling media weight. We demonstrate here how the milling under controlled, prolonged and variable heating programs accomplished in a new milling reactor introduces a new level of mechanochemical reactivity beyond what can be achieved by conventional mechanochemical or solution procedures, and also reduces the time and energy costs of the milling process. The methodology is demonstrated on four varied systems: C–C bond forming Knoevenagel condensation, selective C–N bond formation for amide/urea synthesis, selective double-imine condensation, and solid-state formation of an archetypal open metal-organic framework, MOF-74. The potential of this methodology is best demonstrated on the one-pot selective synthesis of four complex products containing combinations of amide, amine or urea functionalities from the same and simple acyl azide and diamine reactants. Principal control over this enhanced reactivity and selectivity stemmed from the application of specific heating regimes to mechanochemical processing accomplished by a new, in-house developed mechanochemical reactor. As even the moderate increase in temperature strongly affects the selectivity and the rate of mechanochemical reactions, the results presented are in line with recent challenges of the accepted theories of mechanochemical reactivity.