The low-frequency limiting behavior of ambipolar diffusive models of impedance spectroscopy

The Poisson–Nernst–Planck (PNP) diffusional model is a successful theoretical framework to investigate the electrochemical impedance response of insulators containing ionic impurities to an external ac stimulus. Apparent deviations of the experimental spectra from the predictions of the PNP model in the low frequency region are usually interpreted as an interfacial property. Here, we provide a rigorous mathematical analysis of the low-frequency limiting behavior of the model, analyzing the possible origin of these deviation related to bulk properties. The analysis points toward the necessity to consider a bulk effect connected with the difference in the diffusion coefficients of cations and anions (ambipolar diffusion). The ambipolar model does not continuously reach the behavior of the one mobile ion diffusion model when the difference in the mobility of the species vanishes, for a fixed frequency, in the cases of ohmic and adsorption–desorption boundary conditions. The analysis is devoted to the low frequency region, where the electrodes play a fundamental role in the response of the cell; thus, different boundary conditions, charged to mimic the non-blocking character of the electrodes, are considered. The new version of the boundary conditions in the limit in which one of the mobility is tending to zero is deduced. According to the analysis in the dc limit, the phenomenological parameters related to the electrodes are frequency dependent, indicating that the exchange of electric charge from the bulk to the external circuit, in the ohmic model, is related to a surface impedance, and not simply to an electric resistance.

Interfacial Shear at the Atomic Scale

Understanding the interfacial properties between an atomic layer and its substrate is of key interest at both the fundamental and technological level. From Fermi level pinning to strain engineering and superlubricity, the interaction between a single atomic layer and its substrate governs electronic, mechanical, and chemical properties of the layer-substrate system. Here, we measure the hardly accessible interfacial transverse shear modulus of an atomic layer on a substrate. We show that this key interfacial property is critically controlled by the chemistry, order, and structure of the atomic layer-substrate interface. In particular, the experiments demonstrate that the interfacial shear modulus of epitaxial graphene on SiC increases for bilayer films compared to monolayer films, and augments when hydrogen is intercalated between graphene and SiC. The increase in shear modulus for two layers compared to one layer is explained in terms of layer-layer and layer-substrate stacking order, whereas the increase with H-intercalation is correlated with the pinning induced by the H-atoms at the interface. Importantly, we also demonstrate that this modulus is a pivotal measurable property to control and predict sliding friction in supported two-dimensional materials. Indeed, we observe an inverse relationship between friction and interfacial shear modulus, which naturally emerges from simple friction models based on a point mass driven over a periodic potential. This inverse relation originates from a decreased dissipation in presence of large shear stiffness, which reduces the energy barrier for sliding.

Comprehensive study of α-terpineol-loaded oil-in-water (O/W) nanoemulsion: interfacial property, formulation, physical and chemical stability

In this study, the interfacial ability of α-terpineol (α-TOH) was reported, followed by its trapping into oil-in-water (O/W) nanoemulsion as active-ingredient and the long-term observation of this nanosystem influenced by the storage-time (410-days) and temperature (5, 25, 50 °C). The results indicated that the α-TOH can reduce the interfacial tension on the liquid-liquid interface (ΔG°m = −1.81 KJ mol−1; surface density = 8.19 × 10−6 mol m−2; polar head group area = 20.29 Å2), in the absence or presence of surfactant. The O/W nanoemulsion loaded with a high amount of α-TOH (90 mg mL−1; 9α-TOH-NE) into the oil phase was successfully formulated. Among the physical parameters, the mean droplet diameter (MDD) showed a great thermal dependence influenced by the storage-temperature, where the Ostwald ripening (OR) was identified as the main destabilizing phenomena that was taking place on 9α-TOH-NE at 5 and 25 °C along with time. Despite of the physical instability, the integrity of both nanoemulsion at 5 °C and 25 °C was fully preserved up to 410th day, displaying a homogeneous and comparable appearance by visual observation. On contrary, a non-thermal dependence was found for chemical stability, where over 88% of the initial amount of the α-TOH nanoemulsified remained in both 9α-TOH-NE at 5 and 25 °C, up to 410th day. Beyond the key data reported for α-TOH, the importance of this research relies on the long-term tracking of a nanostructured system which can be useful for scientific community as a model for a robust evaluation of nanoemulsion loaded with flavor oils.

Effect of Carbon Fiber Surface Microstructure on Composite Interfacial Property Based on Image Quantitative Characterization Technique

The surface roughness (Ra) and composite interfacial property of carbon fiber (CF) are considered to be mainly affected by the microstructure of the CF surface. However, quantitative characterization of the CF surface microstructure is always a difficulty. How the CF surface microstructure affects the interfacial property of CF composites is not entirely clear. A quantitative characterization technique based on images was established to calculate the cross-section perimeter and area of five types of CFs, as well as the number (N), width (W) and depth (D) of grooves on these CF surfaces. The CF composite interfacial shear strength (IFSS) was tested by the micro-droplet debonding test and modified by the realistic perimeter. The relationship between the groove structure parameter and the Ra, specific surface area and composite interfacial property was discussed in this article. The results indicated that the CF cross-section perimeter calculated by this technique showed strong consistency with the CF specific surface area and composite interfacial property. At last, the composite interface bonding mechanism based on defect capture was put forward. This mechanism can be a guiding principle for CF surface modification and help researchers better understand and establish interface bonding theories.

Chemical computational approaches for optimization of effective surfactants in enhanced oil recovery

The surfactant flooding becomes an attractive method among several Enhanced Oil Recovery (EOR) processes to improve the recovery of residual oil left behind in the reservoir after secondary oil recovery process. The designing of a new effective surfactant is a comparatively complex and often time consuming process as well as cost-effective due to its dependency on the crude oil and reservoir properties. An alternative chemical computational approach is focused in this article to optimize the performance of effective surfactant system for EOR. The molecular dynamics (MD), dissipative particle dynamics (DPD) and density functional theory (DFT) simulations are mostly used chemical computational approaches to study the behaviour in multiple phase systems like surfactant/oil/brine. This article highlighted a review on the impact of surfactant head group structure on oil/water interfacial property like interfacial tensions, interface formation energy, interfacial thickness by MD simulation. The effect of entropy in micelle formation has also discussed through MD simulation. The polarity, dipole moment, charge distribution and molecular structure optimization have been illustrated by DFT. A relatively new coarse-grained method, DPD is also emphasized the phase behaviour of surfactant/oil/brine as well as polymer-surfactant complex system.