Atomistic Insight on Effect of Silica Fume on Intermolecular Interactions between Poly(carboxylate) Superplasticizer and Calcium Ions in Concrete.

Understanding how poly(carboxylate)s of chemical admixtures interact with calcium ions in cement pore solutions in the presence of silica fume is fundamental to developing better chemical admixtures for concrete production. In this work, the intermolecular interactions of calcium ions with a poly(carboxylate) superplasticizer type of chemical admixture was investigated via classical all-atom molecular dynamics (MD) simulations and Density Functional Theory (DFT) calculation methods in the presence of silica fume. The classical all-atom MD simulation and DFT calculation results indicate that calcium ions are interacting with oxygen atoms of the carboxylate group of PCE. The better interaction energy could mean an improved adsorption of the PCE segment with calcium ions. In this regard, it can be noted that the ester-based PCE segment could have a better adsorption onto calcium ions in comparison with the ether-based PCE segment. Moreover, the presence of silicon dioxide could improve the adsorption of the PCE segment onto calcium ions.

Self-Organization Effects of Thin ZnO Layers on the Surface of Porous Silicon by Formation of Energetically Stable Nanostructures.

The formation of complex surface morphology of a multilayer structure, the processes of which are based on quantum phenomena, is a promising domain of the research. A hierarchy of pore of various sizes was determined in the initial sample of porous silicon by the atomic force microscopy. After film deposition by spray pyrolysis, ZnO nanoclusters regularly distributed over the sample surface were formed. Using the electron paramagnetic resonance (EPR) method it was determined that the localization of paramagnetic centers occurs more efficiently as a result of the ZnO deposition. An increase in the number of deposited layers, leads to a decrease in the paramagnetic center relaxation time, which is probably connected with the formation of ZnO nanocrystals with energetically stable properties. The nucleation and formation of nanocrystals is associated with the interaction of particles with an uncompensated charge. There is no single approach to determine the mechanism of this process. By the EPR method supplemented with the signal cyclic saturation, spectral manifestations from individual centers were effectively separated. Based on electron paramagnetic resonance and photoluminescence studies it was revealed that the main transitions between energy levels are due to oxygen vacancies and excitons.

Insight into the glycerol extraction from biodiesel using deep eutectic solvents.

CONTEXT: The main challenge of large-scale biofuel production is related to the extraction of its undesired impurities including glycerol, water, methanol, soap/catalyst, free fatty acids, glycerides, and others. There are many ways to remove glycerol, and herein, the one alternative is the extraction of glycerol from biodiesel by deep eutectic solvents. In this regard, the mixture of a choline chloride (ChCl) and urea, methyltriphenylphosphonium chloride (MTPPCl), and ethylene glycol (EGL), as a deep eutectic solvent (DES), is effective in removing glycerol from biofuel. METHODS: In this work, we have investigated the formation mechanism of ChCl and urea, and then MTPPCl and EGL, as a DES, and then extraction of glycerol from biofuel via DES implementing density functional theory (DFT) by Gaussian09 software, B3LYP basis set, and classical all-atom molecular dynamics (MD) simulations by Gromacs software, GROMOS force field. DFT approximation demonstrates that Cl ion plays an important binding role in the formation of complexes ChCl/urea-based DES + biofuel and in MTPPCl/EGL-based DES + biofuel. We have also considered the formation and change of hydrogen bonds upon the formation of these systems using the DFT method. Large HOMO-LUMO gaps in ChCl/urea-based DES + biofuel and in MTPPCl/urea-based DES + biofuel demonstrate the stability of the complexes. The results of MD work have stated that the chloride ion formed bonding with the choline/ethylene glycol EGL, while still weakly intermolecular interacting with the urea/methyltriphenylphosphonium in ChCl/urea- and MTPPCl/EGL-based DESs. Further results of MD simulations stated that the DESs had a higher intermolecular interaction with glycerol in comparison with biofuel, thereby favoring the extraction process of glycerol from model biofuel. HIGHLIGHTS: • Intermolecular interactions of choline chloride and urea, methyl triphenyl phosphonium chloride, and ethylene glycol-based DESs and their applications in the extraction of glycerol from biofuel studied by DFT calculations and classical all-atom molecular dynamics simulations. • Calculated outputs of DFT calculations and classical all-atom molecular dynamics simulations for DESs and their applications in the extraction of glycerol from biofuel were discussed in detail. • The molecular formation mechanism of choline and methyl triphenyl phosphonium-based DESs and their application in the extraction process of glycerol from biofuel were summarized.