Atomistic simulation of surface functionalization on the interfacial properties of graphene-polymer nanocomposites

Graphene has been increasingly used as nano sized fillers to create a broad range of nanocomposites with exceptional properties. The interfaces between fillers and matrix play a critical role in dictating the overall performance of a composite. However, the load transfer mechanism along graphene-polymer interface has not been well understood. In this study, we conducted molecular dynamics simulations to investigate the influence of surface functionalization and layer length on the interfacial load transfer in graphene polymer nanocomposites. The simulation results show that oxygen-functionalized graphene leads to larger interfacial shear force than hydrogen-functionalized and pristine ones during pull-out process. The increase of oxygen coverage and layer length enhances interfacial shear force. Further increase of oxygen coverage to about 7% leads to a saturated interfacial shear force. A model was also established to demonstrate that the mechanism of interfacial load transfer consists of two contributing parts, including the formation of new surface and relative sliding along the interface. These results are believed to be useful in development of new graphene-based nanocomposites with better interfacial properties.

Tuning the interfacial properties of supported metal nanoclusters

Nanoclusters are objects made up of several to thousands of atoms and form a transitional state of matter between single atoms and bulk materials. Due to their large surface-to-volume ratio, nanoclusters exhibit exciting and yet poorly studied size dependent properties. When deposited directly on bare metal surfaces, the interaction of the cluster with the substrate leads to alteration of the cluster properties, making it less or even non-functional. Surfaces modified with self-assembled monolayers (SAMs) were shown to form an interesting alternative platform, because of the possibility to control wettability by decreasing the surface reactivity and to add functionalities to pre-formed nanoclusters. In this thesis, the underlying size effects and the influence of the nanocluster environment are investigated. The emphasis is on the structural and magnetic properties of nanoclusters and their interaction with thiol SAMs. We report, for the first time, a ferromagnetic-like spin-glass behaviour of uncapped nanosized Au islands tens of nanometres in size. The flattening kinetics of the nanocluster deposition on thiol SAMs are shown to be mediated mainly by the thiol terminal group, as well as the deposition energy and the particle size distribution. On the other hand, a new mechanism for the penetration of the deposited nanoclusters through the monolayers is presented, which is fundamentally different from those reported for atom deposition on alkanethiols. The impinging cluster is shown to compress the thiol layer against the Au surface and subsequently intercalate at the thiol-Au interface. The compressed thiols try then to straighten and push the cluster away from the surface. Depending on the cluster size, this restoring force may or may not enable a covalent cluster-surface bond formation, giving rise to various cluster-surface binding patterns. Compression and straightening of the thiol molecules pinpoint the elastic nature of the SAMs, which has been investigated in this thesis using nanoindentation. The nanoindenation method has been applied to SAMs of varied tail groups, giving insight into the mechanical properties of thiol modified metal surfaces.

Inverse Analysis Determining Interfacial Properties Between Metal Film And Ceramic Substrate With An Adhesive Layer

In the present study, peel tests and inverse analysis were performed to determine the interfacial mechanical parameters for the metal film/ceramic system with an epoxy interface layer between film and ceramic. Al films with a series of thicknesses between 20 and 250 mu m and three peel angles of 90 degrees, 135 degrees and 180 degrees were considered. A finite element model with the cohesive zone elements was used to simulate the peeling process. The finite element results were taken as the training data of a neural network in the inverse analysis. The interfacial cohesive energy and the separation strength can be determined based on the inverse analysis and peel experimental result.

Determination Of Interfacial Properties Between Metal Film And Ceramic Substrate With An Adhesive Layer

Peel test measurements and inverse analysis to determine the interfacial mechanical parameters for the metal film/ceramic system are performed, considering that there exist an epoxy interface layer between film and ceramic. In the present investigation, Al films with a series of thicknesses between 20 and 250 mu m and three peel angles of 90, 135 and 180 degrees are considered. A finite element model with the cohesive zone elements is used to simulate the peel test process. The finite element results are taken as the training data of a neural network in the inverse analysis. The interfacial cohesive energy and the separation strength can be determined based on the inverse analysis and peel experimental result. (C) 2008 Elsevier Ltd. All rights reserved.

Bond and Interfacial Properties of Reinforcement in Self-Compacting Concrete

This paper reports a study carried out to assess the impact of the use of self-compacting concrete (SCC) on bond and interfacial properties around steel reinforcement in practical concrete element. The pull-out tests were carried out to determine bond strength between reinforcing steel bar and concrete, and the depth-sensing nano-indentation technique was used to evaluate the elastic modulus and micro-strength of the interracial transition zone (ITZ) around steel reinforcement. The bond and interracial properties around deformed steel bars in different SCC mixes with strength grades of 35 MPa and 60 MPa (C35, C60) were examined together with those in conventional vibrated reference concrete with the same strength grades. The results showed that the maximum bond strength decreased when the diameter of the steel bar increased from 12 to 20 mm. The normalised bond strengths of the SCC mixes were found to be about 10-40% higher than those of the reference mixes for both bar diameters (12 and 20 mm). The study of the interfacial properties revealed that the elastic modulus and the micro-strength of the ITZ were lower on the bottom side of a horizontal steel bar than on the top side, particularly for the vibrated reference concrete. The difference of ITZ properties between top and bottom side of the horizontal steel bar appeared to be less pronounced for the SCC mixes than for the corresponding reference mixes.

Interfacial Properties of LiTFSI and LiPF6-Based Electrolytes in Binary and Ternary Mixtures of Alkylcarbonates on Graphite Electrodes and Celgard Separator

For a better understanding of the adsorption behavior of alkylcarbonate-based electrolytes on graphite electrodes and Celgard separator for Li-ion batteries applications, the interface parameters are determined by contact angle and surface tension measurements. The correlation between these parameters and chemical compositions made of alkyl carbonate with a varying nature of lithium salts (LiPF6 and LiTFSI) and volume fractions of binary and ternary mixtures containing propylene carbonate (PC), ethylene carbonate (EC), and dimethyl carbonate (DMC) is investigated. From the obtained contact angle and surface tension (?L) values for each liquid, the dispersive and polar components of the surface tension (?Ld and ?Lp) of the electrolyte and interfacial free energy between the solid and liquid (?SL) were then calculated using the Young’s equation. The variation of contact angle (?) and the surface tension, as well as the work of adhesion (WA) of binary PC/DMC mixtures on PP, PE, and PET model surfaces were also measured and commented as function of volume fraction of PC in DMC. Finally, the Zisman’s critical surface tension (?C) for studied surfaces was then obtained showing positives slopes of cos ? versus ?L. This behavior is explained by a relative higher adsorption of alkylcarbonates to the hydrogenated supports or graphite. These results are decisive to understand the performance of electrolyte/electrode material/separator interfaces in lithium-ion battery devices.

On the electrochemical response and interfacial properties of steel–Ca(OH)2 and the steel–concrete system measured using galvanostatic pulses

The interfacial properties of the steel–concrete system are examined via a new approach for evaluation of galvanostatic pulse data. This methodology allows for rapid determination of the corrosion activity of steel, and readily yields values for parameters related to corrosion such as the polarisation resistance and interfacial capacitance. The method of analysis is based on the iterative fitting of a non-exponential model based on a modified Kohlrausch–Williams–Watt (KWW) formalism. The transient behaviour of steel in concrete is non-exponential in its form and, when analysed this way, an exponent β can be determined characterising the exponential non-ideality of the transient. This non-ideality parameter is found to differ significantly for actively corroding and passive specimens, thereby serving as a useful index to the level of corrosion being experienced. Furthermore, the investigation of the interfacial characteristics of the system, previously unobtainable in a reproducible manner via other electrochemical methods, reveal information regarding the kinetic factors governing corrosion of steel in concrete.

Enhancing the interfacial properties of Quickstep{u2122} cured biocomposites

This research has enhanced the performance of natural fibre composites by optimisation of the cure cycle under Quickstep{u2122} process and treatment time under atmospheric pressure glow discharge plasma. The study has also utilised many characterization methods, theoretical models, and established surface-property relationship to manufacture composites with optimum strength and toughness.

A simple and effective method to ameliorate the interfacial properties of cellulosic fibre based bio-composites using poly (ethylene glycol) based amphiphiles

In order to overcome interfacial incompatibility issues in natural fibre reinforced polymer bio-composites, surface modifications of the natural fibres using complex and environmentally unfriendly chemical methods is necessary. In this paper, we demonstrate that the interfacial properties of cellulose-based bio-composites can be tailored through surface adsorption of polyethylene glycol (PEG) based amphiphilic block copolymers using a greener alternative methodology. Mixtures of water or water/acetone were used to form amphiphilic emulsions or micro-crystal suspensions of PEG based amphiphilic block copolymers, and their deposition from solution onto the cellulosic substrate was carried out by simple dip-coating. The findings of this study evidence that, by tuning the amphiphilicity and the type of building blocks attached to the PEG unit, the flexural and dynamic thermo-mechanical properties of cellulose-based bio-composites comprised of either polylactide (PLA) or high density polyethylene (HDPE) as a matrix, can be remarkably enhanced. The trends, largely driven by interfacial effects, can be ascribed to the combined action of the hydrophilic and hydrophobic components of these amphiphiles. The nature of the interactions formed across the fibre-matrix interface is discussed. The collective outcome from this study provides a technological template to significantly improve the performance of cellulose-based bio-composite materials.

Regulation of Sticholysin II-Induced Pore Formation by Lipid Bilayer Composition, Phase State, and Interfacial Properties

Sticholysin II (StnII) is a pore-forming toxin that uses sphingomyelin (SM) as the recognition molecule in targeting membranes.After StnII monomers bind to SM, several toxin monomers act in concert to oligomerize into a functional pore. The regulation of StnII binding to SM, and the subsequent pore-formation process, is not fully understood. In this study, we examined how the biophysical properties of bilayers, originating from variations in the SM structure, from the presence of sterol species, or from the presence of increasingly polyunsaturated glycerophospholipids,affected StnII-induced pore formation. StnII-induced pore formation, as determined from calcein permeabilization, was fastest in the pure unsaturated SM bilayers. In 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC)/saturated SM bilayers (4:1 molar ratio), pore formation became slower as the chain length of the saturated SMs increased from 14 up to 24 carbons. In the POPC/palmitoyl-SM (16:0-SM) 4:1 bilayers, SM could not support pore formation by StnII if dimyristoyl-PC was included at 1:1 stoichiometry with 16:0-SM, suggesting that free clusters of SM were required for toxin binding and/or pore formation. Cholesterol and other sterols facilitated StnII-induced pore formation markedly, but the efficiency did not appear to correlate with the sterol structure. Benzyl alcohol was more efficient than sterols in enhancing the pore-formation process, suggesting that the effect on pore formation originated from alcohol-induced alteration of the hydrogen-bonding network in the SM-containing bilayers. Finally, we observed that pore formation by StnII was enhanced in the PC/16:0-SM 4:1 bilayers, in which the PC was increasingly unsaturated. We conclude that the physical state of bilayer lipids greatly affected pore formation by StnII. Phase boundaries were not required for pore formation, although SM in a gel state attenuated pore formation.

Extended Stoney'S Formula For A Film-Substrate Bilayer With The Effect Of Interfacial Slip

The curvature-stress relation is studied for a film-substrate bilayer with the effect of interfacial slip and compared with that of an ideal interface without interfacial slip. The interfacial slip together with the dimensions, elastic and interfacial properties of the film and substrate layers can cause a significant deviation of curvature-stress relation from that with an ideal interface. The interfacial slip also results in the so-called free edge effect that the stress, constraint force, and curvature vary dramatically around the free edges. The constant curvature as predicted by Stoney's formula and the Timoshenko model of an ideal interface is no longer valid for a bilayer with a nonideal interface. The models with the assumption of an ideal interface can also lead to an erroneous evaluation on the true stress state inside a bilayer with a nonideal interface. The extended Stoney's formula incorporating the effects of both the layer dimensions and interfacial slip is presented.

Effects of self energy of the ions on the double layer structure and properties at the dielectric interface

Although numerous theoretical efforts have been put forth, a systematic, unified and predictive theoretical framework that is able to capture all the essential physics of the interfacial behaviors of ions, such as the Hofmeister series effect, Jones-Ray effect and the salt effect on the bubble coalescence remain an outstanding challenge. The most common approach to treating electrostatic interactions in the presence of salt ions is the Poisson-Boltzmann (PB) theory. However, there are many systems for which the PB theory fails to offer even a qualitative explanation of the behavior, especially for ions distributed in the vicinity of an interface with dielectric contrast between the two media (like the water-vapor/oil interface). A key factor missing in the PB theory is the self energy of the ion.

In this thesis, we develop a self-consistent theory that treats the electrostatic self energy (including both the short-range Born solvation energy and the long-range image charge interactions), the nonelectrostatic contribution of the self energy, the ion-ion correlation and the screening effect systematically in a single framework. By assuming a finite charge spread of the ion instead of using the point-charge model, the self energy obtained by our theory is free of the divergence problems and gives a continuous self energy across the interface. This continuous feature allows ions on the water side and the vapor/oil side of the interface to be treated in a unified framework. The theory involves a minimum set of parameters of the ion, such as the valency, radius, polarizability of the ions, and the dielectric constants of the medium, that are both intrinsic and readily available. The general theory is first applied to study the thermodynamic property of the bulk electrolyte solution, which shows good agreement with the experiment result for predicting the activity coefficient and osmotic coefficient.

Next, we address the effect of local Born solvation energy on the bulk thermodynamics and interfacial properties of electrolyte solution mixtures. We show that difference in the solvation energy between the cations and anions naturally gives rise to local charge separation near the interface, and a finite Galvani potential between two coexisting solutions. The miscibility of the mixture can either increases or decreases depending on the competition between the solvation energy and translation entropy of the ions. The interfacial tension shows a non-monotonic dependence on the salt concentration: it increases linearly with the salt concentration at higher concentrations, and decreases approximately as the square root of the salt concentration for dilute solutions, which is in agreement with the Jones-Ray effect observed in experiment.

Next, we investigate the image effects on the double layer structure and interfacial properties near a single charged plate. We show that the image charge repulsion creates a depletion boundary layer that cannot be captured by a regular perturbation approach. The correct weak-coupling theory must include the self-energy of the ion due to the image charge interaction. The image force qualitatively alters the double layer structure and properties, and gives rise to many non-PB effects, such as nonmonotonic dependence of the surface energy on concentration and charge inversion. The image charge effect is then studied for electrolyte solutions between two plates. For two neutral plates, we show that depletion of the salt ions by the image charge repulsion results in short-range attractive and long-range repulsive forces. If cations and anions are of different valency, the asymmetric depletion leads to the formation of an induced electrical double layer. For two charged plates, the competition between the surface charge and the image charge effect can give rise to like- charge attraction.

Then, we study the inhomogeneous screening effect near the dielectric interface due to the anisotropic and nonuniform ion distribution. We show that the double layer structure and interfacial properties is drastically affected by the inhomogeneous screening if the bulk Debye screening length is comparable or smaller than the Bjerrum length. The width of the depletion layer is characterized by the Bjerrum length, independent of the salt concentration. We predict that the negative adsorption of ions at the interface increases linearly with the salt concentration, which cannot be captured by either the bulk screening approximation or the WKB approximation. For asymmetric salt, the inhomogeneous screening enhances the charge separation in the induced double layer and significantly increases the value of the surface potential.

Finally, to account for the ion specificity, we study the self energy of a single ion across the dielectric interface. The ion is considered to be polarizable: its charge distribution can be self-adjusted to the local dielectric environment to minimize the self energy. Using intrinsic parameters of the ions, such as the valency, radius, and polarizability, we predict the specific ion effect on the interfacial affinity of halogen anions at the water/air interface, and the strong adsorption of hydrophobic ions at the water/oil interface, in agreement with experiments and atomistic simulations.

The theory developed in this work represents the most systematic theoretical technique for weak-coupling electrolytes. We expect the theory to be more useful for studying a wide range of structural and dynamic properties in physicochemical, colloidal, soft-matter and biophysical systems.