Thermodynamics, static properties and transport behaviour of fluids with competing interactions

Competing interaction fluids have become ideal model systems to study a large number of phenomena, for example, the formation of intermediate range order structures, condensed phases not seen in fluids driven by purely attractive or repulsive forces, the onset of particle aggregation under in- and out-of-equilibrium conditions, which results in the birth of reversible and irreversible aggregates or clusters whose topology and morphology depend additionally on the thermodynamic constrictions, and a particle dynamics that has a strong influence on the transport behaviour and rheological properties of the fluid. In this contribution, we study a system of particles interacting through a potential composed by a continuous succession of a short-ranged square-well, an intermediate-ranged square-shoulder and a long-ranged square-well. This potential model is chosen to systematically analyse the contribution of every component of the interaction potential on the phase behaviour, the microstructure, the morphology of the resulting aggregates and the transport phenomena of fluids described by competing interactions. Our results indicate that the inclusion of a barrier and a second well leads to new and interesting effects, which in addition result in variations of the physical properties associated to the competition among interactions.

Thermodynamically Stable Cationic Dimers in Carboxyl-Functionalized Ionic Liquids: The Paradoxical Case of “Anti-Electrostatic” Hydrogen Bonding

We show that carboxyl-functionalized ionic liquids (ILs) form doubly hydrogen-bonded cationic dimers (c+=c+) despite the repulsive forces between ions of like charge and competing hydrogen bonds between cation and anion (c+–a−). This structural motif as known for formic acid, the archetype of double hydrogen bridges, is present in the solid state of the IL 1−(carboxymethyl)pyridinium bis(trifluoromethylsulfonyl)imide [HOOC−CH2−py][NTf2]. By means of quantum chemical calculations, we explored different hydrogen-bonded isomers of neutral (HOOC–(CH2)n–py+)2(NTf2−)2, single-charged (HOOC–(CH2)n–py+)2(NTf2−), and double-charged (HOOC– (CH2)n−py+)2 complexes for demonstrating the paradoxical case of “anti-electrostatic” hydrogen bonding (AEHB) between ions of like charge. For the pure doubly hydrogen-bonded cationic dimers (HOOC– (CH2)n−py+)2, we report robust kinetic stability for n = 1–4. At n = 5, hydrogen bonding and dispersion fully compensate for the repulsive Coulomb forces between the cations, allowing for the quantification of the two equivalent hydrogen bonds and dispersion interaction in the order of 58.5 and 11 kJmol−1, respectively. For n = 6–8, we calculated negative free energies for temperatures below 47, 80, and 114 K, respectively. Quantum cluster equilibrium (QCE) theory predicts the equilibria between cationic monomers and dimers by considering the intermolecular interaction between the species, leading to thermodynamic stability at even higher temperatures. We rationalize the H-bond characteristics of the cationic dimers by the natural bond orbital (NBO) approach, emphasizing the strong correlation between NBO-based and spectroscopic descriptors, such as NMR chemical shifts and vibrational frequencies.

Solutions to a cubic Schrödinger system with mixed attractive and repulsive forces in a critical regime

<abstract><p>We study the existence of solutions to the cubic Schrödinger system</p> <p><disp-formula> <label/> <tex-math id="FE1"> \begin{document}$ -\Delta u_i = \sum\limits_{j = 1}^m \beta_{ij} u_j^2u_i + \lambda_i u_i\ \hbox{in}\ \Omega,\ u_i = 0\ \hbox{on}\ \partial\Omega,\ i = 1,\dots,m, $\end{document} </tex-math></disp-formula></p> <p>when $ \Omega $ is a bounded domain in $ \mathbb R^4, $ $ \lambda_i $ are positive small numbers, $ \beta_{ij} $ are real numbers so that $ \beta_{ii} &gt; 0 $ and $ \beta_{ij} = \beta_{ji} $, $ i\neq j $. We assemble the components $ u_i $ in groups so that all the interaction forces $ \beta_{ij} $ among components of the same group are attractive, i.e., $ \beta_{ij} &gt; 0 $, while forces among components of different groups are repulsive or weakly attractive, i.e., $ \beta_{ij} &lt; \overline\beta $ for some $ \overline\beta $ small. We find solutions such that each component within a given group blows-up around the same point and the different groups blow-up around different points, as all the parameters $ \lambda_i $'s approach zero.</p></abstract>

Application and schemes of induction preliminary heating in magnetic-pulse treatment of metals

The features of the processes of magnetic-pulse processing of metals in traditional schemes of technological processes of modern industrial production are highlighted. The work is a brief description of the state, application, and also proposed induction pre-heating schemes in industrial magnetic-pulse processing of metals. A method for increasing the efficiency of performing specified production operations is considered. The use of preheating leads to a significant improvement in the quality of production operations while reducing energy consumption. New directions of magnetic-pulse processing of metals are noted, implying the transformation of the natural repulsive forces of the metal of the processed object into the forces of magnetic-pulse attraction with a decrease in the operating frequencies of the acting fields. A significant decrease in operating frequencies makes it possible not only to go from repulsion to attraction, but also to go from working with ferromagnetic metals to non-ferromagnetic ones. For example, it becomes possible to attract aluminum blanks. Examples of the use of induction heating of metal blanks in modern industry are given. Various devices used for these operations, offered on the modern market, by both domestic and foreign manufacturers, are considered. The physics of Lenz-Joule heat release is described, the result of which is the induction heating of conductors by Foucault currents in the external electromagnetic field of the instrument. Schemes are proposed for the practical implementation of preliminary induction heating during magnetic-pulse processing of metal blanks, allowing the use of both autonomous devices for exciting eddy currents and a stationary connection, for the same purpose, of an additional source of electricity. As a result of the work, the possibility of increasing the efficiency by increasing the plasticity of the metal when heating the workpiece, as well as possible limitations of the described technology associated with an increase in the active resistance of metals with an increase in the Lenz-Joule heat release is noted.

Sustainable Development of Magnetic Chitosan Core–Shell Network for the Removal of Organic Dyes from Aqueous Solutions

The wide use of alizarin red S (ARS), a typical anthraquinone dye, has led to its continued accumulation in the aquatic environment, which causes mutagenic and carcinogenic effects on organisms. Therefore, this study focused on the removal of ARS dye by adsorption onto a magnetic chitosan core–shell network (MCN). The successful synthesis of the MCN was confirmed by ATR-FTIR, SEM, and EDX analysis. The influence of several parameters on the removal of ARS dye by the MCN revealed that the adsorption process reached equilibrium after 60 min, pH played a major role, and electrostatic interactions dominated for the ARS dye removal under acidic conditions. The adsorption data were described well by the Langmuir isotherm and a pseudo-second order kinetic model. In addition to the preferable adsorption of hydrophobic dissolved organic matter (DOM) fractions onto the MCN, the electrostatic repulsive forces between the previously adsorbed DOM onto MCN and ARS dye resulted in lower ARS dye removal. Furthermore, the MCN could easily be regenerated and reused for up to at least five cycles with more than 70% of its original efficiency. Most importantly, the spent MCN was pyrolytically converted into N-doped magnetic carbon and used as an adsorbent for various dyes, thus establishing a waste-free adsorption process.

New Insights into Surfactant Adsorption Estimation During ASP Flooding in Carbonates Under Harsh Conditions Using Surface Complexation Modeling

Several laboratory experiments demonstrated that the use of sodium hydroxide could increase the solution pH and reduce the adsorption of anionic surfactants. However, a better understanding of rock-oil-brine interactions and their effect on surfactant adsorption during alkaline-surfactant-polymer (ASP) flooding is needed for realistic and representative estimations of surfactant adsorption levels. Therefore, this study presents a novel approach to capture these interactions and better predict their effect on surfactant adsorption as well as effluent concentrations of surfactant and various aqueous species. Currently, surface complexation models (SCM) consider rock-brine, oil-brine, and surfactant-brine reactions. In this work, four new surface complexation reactions with intrinsic stability constants that honor oil-surfactant interactions have been proposed for the first time and then validated against experimental data reported in the literature. In addition, we analyzed the effect of various parameters on surface adsorption under harsh conditions of high-temperature and high-salinity using the proposed surface complexation model (SCM). The results showed that the developed surfactant-based SCM is robust and accurate for estimating surfactant adsorption and its concentration in the effluent during chemical floods. The model was validated against two sets of ASP corefloods from the literature including single-phase and two-phase dynamic surfactant adsorption studies. The findings highlighted that oil-surfactant surface complexation reactions are important and should be captured for more representative and accurate estimation of surfactant adsorption during chemical flooding. Moreover, the detail and comprehensive analysis showed that surfactant adsorption increases and its concentration in the effluent decreases with the increase in temperature of the chemical flood, which could be due to the increase in kinetic energy of the species. It was also showed that a decrease in water total salinity decreases the surfactant adsorption on the rock surface, which is related to the increase in the repulsive forces between the adsorbed species. Additionally, with the increase in surfactant concentration in the chemical flood, the effluent surfactant concertation increases, with a slight increase in surfactant adsorption. This slight increase in adsorption can be neglected compared to the injected and produced masses of the surfactant that are proportional. Moreover, the effect of sulfate spiking is significant where the increase in sulfate concentration reduces the surfactant adsorption. Furthermore, it is worth highlighting that the lowest surfactant adsorption levels were achieved through injected water dilution; less than 0.1 mg/g of rock. This is the first study to test a novel formulation of surface complexation modeling considering oil-surfactant effect on surfactant adsorption properties. The proposed framework to estimate surfactant adsorption is conducted for high-temperature and high-salinity reservoir condition. Thus, it could be used in numerical reservoir simulators to estimate oil recovery due to wettability alteration by chemical flooding in carbonates, which will be investigated in our future work. The surfactant adsorption mechanisms during chemical flooding is very case-dependent and hence, the findings of this study cannot be generalized.

An Integrated Study of Water Weakening and Fluid Rock Interaction Processes in Porous Rocks: Linking Mechanical Behavior to Surface Properties

We investigated the impact of water weakening on the mechanical behavior of Obourg Chalk and Ciply Chalk (Mons Basin, Belgium). Different mechanical tests were conducted to estimate the unconfined compressive strength (UCS), tensile strength, Young’s modulus, mechanical strength under triaxial loading, critical pressure, fracture toughness, cohesion, and internal friction coefficient on samples either dry or saturated with water or brine. This extensive dataset allowed us to calculate wet-to-dry ratios (WDR), i.e., the ratio between any property for a dry sample to that for the water-saturated sample. For both chalks, we found that water has a strong weakening effect with WDR ranging from 0.4 to 0.75. Ciply Chalk exhibits more water weakening than Obourg Chalk. The highest water weakening effect was obtained for UCS, critical pressure, and Young’s modulus. Weakening effects are still present in brine-saturated samples but their magnitude depends on the fluid composition. The mechanical data were correlated to variations in surface energy derived from three different methods: fracture mechanics, contact angle goniometry, and atomic force microscopy. Water weakening in the tested chalks can be explained by a clear reduction in surface energy and by the existence of repulsive forces which lower the cohesion.

Citric acid/β-alanine carbon dots as a novel tool for delivery of plasmid DNA into E. coli cells

Successful delivery of plasmid DNA into the microbial cells is fundamental in recombinant DNA technology. Natural bacterial transformation is limited to only certain species due in part to the repulsive forces between negatively charged DNA and bacterial membranes. Most common method of DNA delivery into bacteria is artificial transformation through heat shock and electroporation. These methods require sophisticated instruments and tedious steps in preparation of competent cells. Transformation by conjugation is also not applicable to all plasmids. Nanoparticles have been used successfully in therapeutics for drug delivery into animal cells. They are starting to gain popularity in plant sciences as novel DNA nano carriers. Despite their promise as tool for DNA delivery, their use in microbial cell transformation has not been reported yet. Here we report the synthesis of carbon dots (CDs) from citric acid and β-alanine and their use in DNA delivery into E. coli cells. CDs were fabricated using microwave assisted synthesis. Plasmids carrying RFP reporter and ampicillin resistance genes were transferred to bacterial cells and further confirmed using polymerase chain reaction. Our findings indicate that CDs can be used successfully for delivery of foreign DNA of up to 10 kb into E. coli. We have demonstrated the use of β-alanine/citric acid carbon dots as nanocarriers of DNA into E. coli cells and identified their limitation in terms of the size of plasmid DNA they could carry. Use of these carbon dots is a novel method in foreign DNA delivery into bacterial cells and have a potential for the transformation of resistant organism for which there is still no reliable DNA delivery systems.

Point Cloud Resampling by Simulating Electric Charges on Metallic Surfaces

3D point cloud resampling based on computational geometry is still a challenging problem. In this paper, we propose a point cloud resampling algorithm inspired by the physical characteristics of the repulsion forces between point electrons. The points in the point cloud are considered as electrons that reside on a virtual metallic surface. We iteratively update the positions of the points by simulating the electromagnetic forces between them. Intuitively, the input point cloud becomes evenly distributed by the repulsive forces. We further adopt an acceleration and damping terms in our simulation. This system can be viewed as a momentum method in mathematical optimization and thus increases the convergence stability and uniformity performance. The net force of the repulsion forces may contain a normal directional force with respect to the local surface, which can make the point diverge from the surface. To prevent this, we introduce a simple restriction method that limits the repulsion forces between the points to an approximated local plane. This approach mimics the natural phenomenon in which positive electrons cannot escape from the metallic surface. However, this is still an approximation because the surfaces are often curved rather than being strict planes. Therefore, we project the points to the nearest local surface after the movement. In addition, we approximate the net repulsion force using the K-nearest neighbor to accelerate our algorithm. Furthermore, we propose a new measurement criterion that evaluates the uniformity of the resampled point cloud to compare the proposed algorithm with baselines. In experiments, our algorithm demonstrates superior performance in terms of uniformization, convergence, and run-time.

A New Multidimensional Repulsive Potential Field to Avoid Obstacles by Nonholonomic UAVs in Dynamic Environments

The ability of autonomous flight with obstacle avoidance should be a fundamental feature of all modern unmanned aerial vehicles (UAVs). The complexity and difficulty of such a task, however, significantly increase in cases combining moving obstacles and nonholonomic UAVs. Additionally, since they assume the symmetrical distribution of repulsive forces around obstacles, traditional repulsive potential fields are not well suited for nonholonomic vehicles. The limited maneuverability of these types of UAVs, including fixed-wing aircraft, requires consideration not only of their relative position, but also their speed as well as the direction in which the obstacles are moving. To address this issue, the following work presents a novel multidimensional repulsive potential field dedicated to nonholonomic UAVs. This field generates forces that repulse the UAV not from the obstacle’s geometrical center, but from areas immediately behind and in front of it located along a line defined by the obstacle’s velocity vector. The strength of the repulsive force depends on the UAV’s distance to the line representing the obstacle’s movement direction, distance to the obstacle along that line, and the relative speed between the UAV and the obstacle projected to the line, making the proposed repulsive potential field multidimensional. Numerical simulations presented within the paper prove the effectiveness of the proposed novel repulsive potential field in controlling the flight of nonholonomic UAVs.