Interfacial properties of asphaltenes at toluene-water interfaces.

Asphaltenes are "n-alkane insoluble" species in crude oil that stabilize water-in-oil emulsions. To understand asphaltene adsorption mechanisms at oil-water interfaces and coalescence blockage, we first studied the behavior in aliphatic oil-water systems in which asphaltenes are almost insoluble. They adsorbed as monomers, giving a unique master curve relating interfacial tension (IFT) to interfacial coverage through a Langmuir equation of state (EoS). The long-time surface coverage was independent of asphaltene bulk concentration and asymptotically approached the 2-D packing limit for polydisperse disks. On coalescence, the surface coverage exceeded the 2-D limit and the asphaltene film appeared to become solidlike, apparently undergoing a transition to a soft glassy material and blocking further coalescence. However, real systems consist of mixtures of aliphatic and aromatic components in which asphaltenes may be quite soluble. To understand solubility effects, we focus here on how the increased bulk solubility of asphaltenes affects their interfacial properties in comparison to aliphatic oil-water systems. Unlike the "almost irreversible" adsorption of asphaltenes where the asymptotic interfacial coverage was independent of the bulk concentration, an equilibrium surface pressure, dependent on bulk concentration, was obtained for toluene-water systems because of adsorption being balanced by desorption. The equilibrium surface coverage could be obtained from the short- and long-term Ward-Tordai approximations. The behavior of the equilibrium surface pressure with the equilibrium surface coverage was then derived. These data for various asphaltene concentrations were used to determine the EoS, which for toluene-water could also be fitted by the Langmuir EoS with Γ∞ = 3.3 molecule/nm(2), the same value as that found for these asphaltenes in aliphatic media. Asphaltene solubility in the bulk phase only appears to affect the adsorption isotherm but not the EoS. Further support for these observations is provided by dilatational rheology experiments for the EoS and contraction experiments in which desorption to the equilibrium surface pressure was observed.

Long-term adsorption kinetics of asphaltenes at the oil-water interface: a random sequential adsorption perspective.

Previous studies indicated that asphaltenes adsorbed as monomers on oil-water interfaces and the early stage kinetics of the process was controlled by diffusion and hence dependent on oil viscosity. By measuring interfacial tension (IFT) as a function of surface coverage during droplet expansions in pendant drop experiments, it was also concluded that the IFT data could be interpreted with a Langmuir equation of state (EoS), which was independent of oil viscosity, time of adsorption, and bulk asphaltenes concentration. The surface excess coverage was calculated to be ∼0.3 nm(2)/molecule, which suggested adsorption in face-on configuration of asphaltenes monomers at the interface and average PAH core per molecule of about 6 for the asphaltenes investigated, consistent with the Yen-Mullins model. The current study focuses on the kinetics of asphaltenes adsorption at longer times and higher interfacial coverage. Long-term IFT data have been measured by the pendant drop method for different asphaltenes concentrations and for different bulk viscosities of the oil phase (0.5-28 cP). The data indicate that when coverage reaches 35-40%, the adsorption rates slow down considerably compared to the diffusion-controlled rates at the very early stages. The surface pressure increase rate (or IFT decrease rate) at these higher coverages is now independent of oil viscosity but dependent upon both surface pressure itself and asphaltene monomer concentration. The long-term asymptotic behavior of surface coverage is found to be consistent with the predictions from surface diffusion-mediated random sequential adsorption (RSA) theory which indicates a linear dependency of surface coverage on 1/√t and an asymptotic limit very close to 2D random close packing of polydispersed disks (85%). From these observations RSA theory parameters were extracted that enabled description of adsorption kinetics for the range of conditions above surface coverage of 35%.

Interfacial rheology of asphaltenes at oil-water interfaces and interpretation of the equation of state.

In an earlier study, oil-water interfacial tension was measured by the pendant drop technique for a range of oil-phase asphaltene concentrations and viscosities. The interfacial tension was found to be related to the relative surface coverage during droplet expansion. The relationship was independent of aging time and bulk asphaltenes concentration, suggesting that cross-linking did not occur at the interface and that only asphaltene monomers were adsorbed. The present study extends this work to measurements of interfacial rheology with the same fluids. Dilatation moduli have been measured using the pulsating droplet technique at different frequencies, different concentrations (below and above CNAC), and different aging times. Care was taken to apply the technique in conditions where viscous and inertial effects are small. The elastic modulus increases with frequency and then plateaus to an asymptotic value. The asymptotic or instantaneous elasticity has been plotted against the interfacial tension, indicating the existence of a unique relationship, between them, independent of adsorption conditions. The relationship between interfacial tension and surface coverage is analyzed with a Langmuir equation of state. The equation of state also enabled the prediction of the observed relationship between the instantaneous elasticity and interfacial tension. The fit by a simple Langmuir equation of state (EOS) suggests minimal effects of aging and of nanoaggregates or gel formation at the interface. Only one parameter is involved in the fit, which is the surface excess coverage Γ∞ = 3.2 molecules/nm(2) (31.25 Å(2)/molecule). This value appears to agree with flat-on adsorption of monomeric asphaltene structures consisting of aromatic cores composed of an average of six fused rings and supports the hypothesis that nanoaggregates do not adsorb on the interface. The observed interfacial effects of the adsorbed asphaltenes, correlated by the Langmuir EOS, are consistent with the asphaltene aggregation behavior in the bulk fluid expected from the Yen-Mullins model.

Macroscopic investigation of water volume effects on interfacial dynamic behaviors between clathrate hydrate and water.

This study investigated the effects of the water volume on the interfacial dynamics between cyclopentane (CP) hydrate and water droplet in a CP/n-decane oil mixture. The adhesion force between CP hydrate and various water droplets was determined using the z-directional microbalance. Through repetition of precise measurements over several cycles from contact to detachment, we observed abnormal wetting behaviors in the capillary bridge during the retraction process when the water drop volume is larger than 100 µL. With the increase in water droplet volumes, the contact force between CP hydrate and water also increases up to 300 µL. However, there is a dramatic reduction of increasing rate in the contact forces over 300 µL of water droplet. With the addition of the surfactants of sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium bromide (DTAB) to the water droplet, the contact force between CP hydrate and solution droplet exhibits a lower value and a transition volume of the contact force comes with a smaller solution volume of 200 µL. The water volume effects on the liquid wetting of the probe and the size of capillary bridges provide important insight into hydrate growth and aggregation/agglomeration in the presence of free water phase inside gas/oil pipelines.

Adsorption kinetics of asphaltenes at the oil-water interface and nanoaggregation in the bulk.

Asphaltenes constitute high molecular weight constituents of crude oils that are insoluble in n-heptane and soluble in toluene. They contribute to the stabilization of the water-in-oil emulsions formed during crude oil recovery and hinder drop-drop coalescence. As a result, asphaltenes unfavorably impact water-oil separation processes and consequently oil production rates. In view of this there is a need to better understand the physicochemical effects of asphaltenes at water-oil interfaces. This study elucidates aspects of these effects based on new data on the interfacial tension in such systems from pendant drop experiments, supported by results from nuclear magnetic resonance (NMR) and dynamic light scattering (DLS) studies. The pendant drop experiments using different asphaltene concentrations (mass fractions) and solvent viscosities indicate that the interfacial tension reduction kinetics at short times are controlled by bulk diffusion of the fraction of asphaltenes present as monomer. At low mass fractions much of the asphaltenes appear to be present as monomers, but at mass fractions greater than about 80 ppm they appear to aggregate into larger structures, a finding consistent with the NMR and DLS results. At longer times interfacial tension reduction kinetics are slower and no longer diffusion controlled. To investigate the controlling mechanisms at this later stage the pendant drop experiment was made to function in a fashion similar to a Langmuir trough with interfacial tension being measured during expansion of a droplet aged in various conditions. The interfacial tension was observed to depend on surface coverage and not on time. All observations indicate the later stage transition is to an adsorption barrier-controlled regime rather than to a conformational relaxation regime.

Direct measurements of contact force between clathrate hydrates and water.

A method for precise and reproducible initial contact force measurements is introduced utilizing an apparatus fabricated with a microbalance and z-axis stage to study the interaction behavior between cyclopentane (CP) hydrate and water in a temperature controlled hydrocarbon environment. CP hydrate probes are prepared using hydrate slurries composed of 5 wt % CP and Wilhelmy rods. The CP hydrate probe is slowly brought into contact with water to determine the initial contact force. The effect of substrate morphology on the initial contact force is reported through employing aluminum substrates prepared using physical vapor deposition (PVD) and milling. Accurate and facile measurements are performed by applying a high-resolution microbalance with 0.1 microN resolution to provide repeatable and consistent results of initial contact force between hydrate and water.

Investigation of macroscopic interfacial dynamics between clathrate hydrates and surfactant solutions.

Macroscopic interfacial interactions between cyclopentane (CP) hydrates and various surfactants droplets are examined in a CP/n-decane oil mixture. Initial contact force and subsequent z-axis dependent retraction force are measured utilizing a high-resolution microbalance integrated with a micrometer-precision stage. The resulting retraction force is utilized to determine the overall adhesion energy of the system. In addition, interfacial tensions and contact angles of the system are examined to further understand the effect of surface-active agents and substrates on the initial contact and retraction forces.

A molecular dynamics study of the motion of a nanodroplet of pure liquid on a wetting gradient.

The dynamic behavior of a nanodroplet of a pure liquid on a wetting gradient was studied using molecular dynamics simulation. The spontaneous motion of the droplet is induced by a force imbalance at the contact line. We considered a Lennard-Jones system as well as water on a self-assembled monolayer (SAM). The motion of the droplet for the Lennard-Jones case was found to be steady with a simple power law describing its center-of-mass position with time. The behavior of the water droplet was found to depend on the uniformity of the wetting gradient, which was composed of methyl- and hydroxyl-terminated alkanethiol chains on Au(111). When the gradient was nonuniform the droplet was found to become pinned at an intermediate position. However, a uniform gradient with the same overall strength was found to drive a droplet consisting of 2000 water molecules a distance of 25 nm or nearly ten times its initial base radius in tens of nanoseconds. A similar result was obtained for a droplet that was twice as large. Despite the many differences between the Lennard-Jones and water-SAM systems, the two show a similar overall behavior for the motion. Fair agreement was seen between the simulation results for the water droplet speed and the theoretical predictions. When the driving force was corrected for contact angle hysteresis, the agreement was seen to improve.

Electrostatically assisted fabrication of silver-dielectric core/shell nanoparticles thin film capacitor with uniform metal nanoparticle distribution and controlled spacing.

An electrostatically-assisted strategy for fabrication of thin film composite capacitors with controllable dielectric constant (k) has been developed. The capacitor is composed of metal-dielectric core/shell nanoparticle (silver/silica, Ag@SiO2) multilayer films, and a backfilling polymer. Compared with the simple metal particle-polymer mixtures where the metal nanoparticles (NP) are randomly dispersed in the polymer matrix, the metal volume fraction in our capacitor was significantly increased, owing to the densely packed NP multilayers formed by the electrostatically assisted assembly process. Moreover, the insulating layer of silica shell provides a potential barrier that reduces the tunneling current between neighboring Ag cores, endowing the core/shell nanocomposites with a stable and relatively high dielectric constant (k) and low dielectric loss (D). Our work also shows that the thickness of the SiO2 shell plays a dominant role in controlling the dielectric properties of the nanocomposites. Control over metal NP separation distance was realized not only by variation the shell thickness of the core/shell NPs but also by introducing a high k nanoparticle, barium strontium titanate (BST) of relatively smaller size (∼8nm) compared to 80-160nm of the core/shell Ag@SiO2 NPs. The BST assemble between the Ag@SiO2 and fill the void space between the closely packed core/shell NPs leading to significant enhancement of the dielectric constant. This electrostatically assisted assembly method is promising for generating multilayer films of a large variety of NPs over large areas at low cost.

Understanding the lateral movement of particles adsorbed at a solid-liquid interface.

In this paper we study the phenomenon of lateral movement of particles that are electrostatically adsorbed at a solid-liquid interface. The experimental system involves negatively charged silica particles of two different sizes (65 nm and 90 nm) that are exposed to the positively charged solid surface (silane coated silicon wafer) in sequential steps. The particle-adsorbed wafers are analyzed under a scanning electron microscope and the images are processed to determine the pair-correlation function for the particles adsorbed in the first step. From the pair correlation data and the particle surface coverage data we show that the adsorbed particles are mobile at the solid-liquid interface. In specific, we show that the adsorbed particles are mobile at the solid-liquid interface when there is a driving force for the adsorbed particles to move. The driving force in the scheme of experiments discussed in this paper is the reduction in the free energy of the system.

Measurement of the kinetic rate constants for the adsorption of superspreading trisiloxanes to an air/aqueous interface and the relevance of these measurements to the mechanism of superspreading.

Super-spreading trisiloxane surfactants are a class of amphiphiles which consist of nonpolar trisiloxane headgroups ((CH3)3-Si-O)2-Si(CH3)(CH2)3-) and polar parts composed of between four and eight ethylene oxides (ethoxylates, -OCH2CH2-). Millimeter-sized aqueous drops of trisiloxane solutions at concentrations well above the critical aggregate concentration spread rapidly on very hydrophobic surfaces, completely wetting out at equilibrium. The wetting out can be understood as a consequence of the ability of the trisiloxanes at the advancing perimeter of the drop to adsorb at the air/aqueous and aqueous/hydrophobic solid interfaces and to reduce considerably the tensions of these interfaces, creating a positive spreading coefficient. The rapid spreading can be due to maintaining a positive spreading coefficient at the perimeter as the drop spreads. However, the air/aqueous and solid/aqueous interfaces at the perimeter are depleted of surfactant by interfacial expansion as the drop spreads. The spreading coefficient can remain positive if the rate of surfactant adsorption onto the solid and fluid surfaces from the spreading aqueous film at the perimeter exceeds the diluting effect due to the area expansion. This task is made more difficult by the fact that the reservoir of surfactant in the film is continually depleted by adsorption to the expanding interfaces. If the adsorption cannot keep pace with the area expansion at the perimeter, and the surface concentrations become reduced at the contact line, a negative spreading coefficient which retards the drop movement can develop. In this case, however, a Marangoni mechanism can account for the rapid spreading if the surface concentrations at the drop apex are assumed to remain high compared to the perimeter so that the drop is pulled out by the higher tension at the perimeter than at the apex. To maintain a high apex concentration, surfactant adsorption must exceed the rate of interfacial dilation at the apex due to the outward flow. This is conceivable because, unlike that at the contact line, the surfactant reservoir in the liquid at the drop center is not continually depleted by adsorption onto an expanding solid surface. In an effort to understand the rapid spreading, we measure the kinetic rate constants for adsorption of unaggregated trisiloxane surfactant from the sublayer to the air/aqueous surface. The kinetic rate of adsorption, computed assuming the bulk concentration of monomer to be uniform and undepleted, represents the fastest that surfactant monomer can adsorb onto the air/aqueous surface in the absence of direct adsorption of aggregates. The kinetic constants are obtained by measuring the dynamic tension relaxation as trisiloxanes adsorb onto a clean pendant bubble interface. We find that the rate of kinetic adsorption is only of the same order as the area expansion rates observed in superspreading, and therefore the unaggregated flux cannot maintain very high surface concentrations at the air/aqueous interface, either at the apex or at the perimeter. Hence in order to maintain either a positive spreading coefficient or a Marangoni gradient, the surfactant adsorptive flux needs to be augmented, and the direct adsorption of aggregates (which in the case of the trisiloxanes are bilayers and vesicles) is suggested as one possibility.

Experimental studies on irreversibility of electrostatic adsorption of silica nanoparticles at solid-liquid interface.

Adsorption of colloidal nanoparticles (NPs) at solid-liquid interface is a scientifically interesting and technologically important phenomenon due to its fundamental importance in many industrial, environmental, and biological processes, such as wastewater treatment, printing, coating of surfaces, chromatography, papermaking, or biocompatibility. The process is well understood theoretically by the random sequential adsorption (RSA) model, based on the assumption of irreversible adsorption. Irreversible adsorption is defined as a process in which, once adsorbed, a particle can neither desorb, nor to move laterally on the surface. However, published experimental data that verifies the irreversibility of particle adsorption are very limited. In this study, we demonstrate the irreversibility of electrostatically driven nanoparticle adsorption utilizing a carefully selected set of experiments. A simple method was employed by uniquely introducing Ag@SiO2 core/shell NPs to perform exchange adsorptions experiments. Stöber SiO2 NPs with a diameter of 50-80 nm were initially electrostatically adsorbed onto amino-functionalized silicon wafer substrates followed by the subsequent adsorption of Ag@SiO2 NPs. The Ag@SiO2 NPs have the same surface chemistry as the neat SiO2 NPs. For the second step the adsorption time was varied from 1 min to 1 week so as to get a thorough understanding of the process irreversibility. Surface coverage quantification has shown that the surface coverage of the initially adsorbed SiO2 NPs stays the same independent of the duration of the second step adsorption using the Ag@SiO2 core/shell NPs. This observation directly confirms the irreversibility of electrostatic adsorption of NPs.

Influence of particle/solid surface zeta potential on particle adsorption kinetics.

In this paper we attempt to understand monolayer formation of spherical particles on a solid surface immersed in a suspension and driven by electrostatic interaction force. The study focuses on the theoretical aspects of the particle adsorption and modeling work based on the random sequential adsorption (RSA) approach is done in order to describe the particle adsorption kinetics and the saturation coverage. The theoretical model is then compared with experimental data obtained under conditions similar to those of the modeling work. Studying the adsorption of polystyrene particles on a silicon wafer in an aqueous system was employed to experimentally validate the theoretical framework. It has been shown both theoretically and experimentally that the particle and solid surface zeta potential values do influence the adsorption kinetics but the effect is too negligible to be of any use in accelerating the kinetics. We have shown that the electrostatically driven particle adsorption is a transport limited process and the rate of transport is not a major function of the zeta potential values of the particle and the solid surface. The faster kinetics seen when the ionic concentration of the suspension is increased is because of the blocking effects and not due to faster approach of particles towards the solid surface. Finally, we have made an important addition to the existing models by incorporating the variation in the flux as a function of particle/solid surface zeta potentials, surface coverage and the randomized position of incidence of an incoming particle on the solid surface.

Hollandites as a new class of multiferroics.

Discovery of new complex oxides that exhibit both magnetic and ferroelectric properties is of great interest for the design of functional magnetoelectrics, in which research is driven by the technologically exciting prospect of controlling charges by magnetic fields and spins by applied voltages, for sensors, 4-state logic, and spintronics. Motivated by the notion of a tool-kit for complex oxide design, we developed a chemical synthesis strategy for single-phase multifunctional lattices. Here, we introduce a new class of multiferroic hollandite Ba-Mn-Ti oxides not apparent in nature. BaMn3Ti4O14.25, designated BMT-134, possesses the signature channel-like hollandite structure, contains Mn(4+) and Mn(3+) in a 1:1 ratio, exhibits an antiferromagnetic phase transition (TN ~ 120 K) with a weak ferromagnetic ordering at lower temperatures, ferroelectricity, a giant dielectric constant at low frequency and a stable intrinsic dielectric constant of ~200 (1-100 MHz). With evidence of correlated antiferromagnetic and ferroelectric order, the findings point to an unexplored family of structures belonging to the hollandite supergroup with multifunctional properties, and high potential for developing new magnetoelectric materials.

Electrostatically driven adsorption of silica nanoparticles on functionalized surfaces.

Adsorption of nanoparticles on solid supports is a scientifically interesting and technologically important phenomenon that has been attracting ever-increasing attention. Formation of particle-based films onto surfaces from stable suspensions is at the center of the development of new devices that utilize the plethora of newly synthesized nanoparticles with exciting properties. In this study we exploit the attractive electrostatic interactions between silica (SiO(2)) nanoparticles and functionalized substrates that display an amine termination in order to devise a simple method for the fabrication of SiO(2) nanoparticle films. Electrostatically controlled adsorption allows for uniform coverage of nanoparticles over large areas. The Stöber method (a sol-gel approach) was employed to prepare uniformly sized SiO(2) nanoparticles with a diameter of 50-80 nm. Native oxide-covered silicon wafer substrates were amino-functionalized utilizing the self-assembled monolayer of 3-aminopropyltrimethoxysilane (APS). The adsorption of SiO(2) nanoparticle film onto the silicon wafer substrate was controlled by modulation of the electrostatic interaction between nanoparticles and the substrate. Modification of surface charge of either the SiO(2) NP or the substrate is a crucial step in the process. Thus the effect of APS adsorption time on the surface energy of the substrate was investigated. Also, process parameters such as NP concentration and solvent composition were varied in order to investigate the extent of NP adsorption. Moreover, NaCl was introduced to the SiO(2) suspension as a charge-screening agent to reduce the inter-particle repulsion in the suspension as well as interaction of the particles with the surface. This resulted in denser/thicker films.

Facile synthesis of silver core - silica shell composite nanoparticles.

Combining metal nanoparticles and dielectrics (e.g. silica) to produce composite materials with high dielectric constant is motivated by application in energy storage. Control over dielectric properties and their uniformity throughout the composite material is best accomplished if the composite is comprised of metal core - dielectric shell structured nanoparticles with tunable dimensions. We have synthesized silver nanoparticles in the range of 40-100nm average size using low concentration of saccharide simultaneously as the reducing agent and electrostatic stabilizer. Coating these silver particles with silica from tetraalkoxysilanes has different outcomes depending on the alcoholic solvent and the silver particle concentration. A common issue in solution-based synthesis of core-shell particles is heterogeneous nucleation whereupon two populations are formed: the desired core-shell particles and undesired coreless particles of the shell material. We report the formation of Ag@SiO(2) core-shell particles without coreless silica particles as the byproduct in 2-propanol. In ethanol, it depends on the silver surface area available whether homogeneous nucleation of silica on silver is achieved. In methanol and 1-butanol, core-shell particles did not form. This demonstrates the significance of controlling the tetraalkoxysilane hydrolysis rate when growing silica shells on silver nanoparticles.

Spectral bar coding of polystyrene microbeads using multicolored quantum dots.

This paper focuses on encoding polystyrene microbeads, 10-100 microm in diameter, with a luminescent spectral bar code composed of mixtures of quantum dots (QDs) emitting at different wavelengths (colors). The QDs are encapsulated in the bead interior during the bead synthesis using a suspension polymerization, and the bar code is constructed by varying both the number of colors included in the bead and, for each color, the number of QDs of that color. Confocal laser scanning microscopy images of the beads demonstrate that the multicolored QDs are pushed together into inclusions within the bead interior. The encoded bead emission spectrum indicates that the peak position of the included colors does not shift relative to the corresponding peaks of the spectra recorded for the nonaggregated QDs at identical loading concentrations. Due to the spatial proximity of the QDs in the inclusions, electronic energy transfer from the lower wavelength emitting QDs to the higher emitting QDs changes the relative intensities of the colors compared to the values in the nonaggregated spectra. We show that this energy transfer does not obscure the spectral uniqueness of the different codes. Ratiometric encoding, in which the bar code is read as relative color intensity, is shown to remove the dependence of the code on the bead size.

Arraying of intact liposomes into chemically functionalized microwells.

Here, we describe a protocol to bind individual, intact phospholipid bilayer liposomes, which are on the order of 1 microm in diameter, in microwells etched in a regular array on a silicon oxide substrate. The diameter of the wells is on the order of the liposome diameter, so only one liposome is located in each well. The background of the silicon oxide surface is functionalized with a PEG oligomer using the contact printing of a PEG silane to present a surface that resists the adsorption of proteins, lipid material, and liposomes. The interiors of the wells are functionalized with an aminosilane to facilitate the conjugation of biotin, which is then bound to Neutravidin. The avidin-coated well interiors bind the liposomes whose surfaces contain biotinylated lipids. The specific binding of the liposomes to the surface using the biotin-avidin linkage, together with the resistant nature of the background and the physical confinement of the wells, allows the liposomes to remain intact and to not unravel, rupture, and fuse onto the surface. We demonstrate this intact arraying using confocal laser scanning microscopy of fluorophores specifically tagging the microwells, the lipid bilayer, and the aqueous interior of the liposome.

Molecular dynamics study of the influence of surfactant structure on surfactant-facilitated spreading of droplets on solid surfaces.

The spreading of a partially wetting aqueous drop in air on a hydrophobic surface can be facilitated by the adsorption of surfactants from the drop phase onto the air/aqueous and aqueous/hydrophobic solid interfaces of the drop. At the contact line at which these interfaces meet, conventional surfactants with a linear alkyl hydrophobic chain attached to a polar group adsorb onto the surfaces, forming monolayers which remain distinct as they merge at the contact juncture. The adsorption causes a decrease in the interfacial tensions and reduction in the contact angle but the angle remains above zero so the drop is still nonwetting. Trisiloxane surfactants with a T-shaped geometry in which the hydrophobic group is composed of a trisiloxane oligomer with a polar group attached at the center of the chain can give rise to a zero contact angle at the contact line and complete wetting (superspreading). Experimental evidence suggests the adsorption of the T-shaped molecule, in addition to significantly decreasing the tensions of the interfaces (relative to the conventional surfactants), promotes the formation of a precursor film consisting of a surfactant bilayer at the contact line which facilitates the spreading. The aim of this study is to use molecular dynamics to examine if the T-shaped structure can promote spreading by the formation of a bilayer and to contrast this case with that of the linear chain surfactant where complex assembly does not occur. The simulation models the solvent as a monatomic liquid, the substrate as a particle lattice, and the surfactants as united atom structures, with all interactions given by Lennard-Jones potentials. We start with a base case in which the solvent partially wets a substrate comprised of a lattice of particles. We demonstrate that adsorbed T-shaped surfactant monolayers can, when the interaction between the solvent and the hydrophile particles is strong enough, assemble into a bilayer, allowing the drop to extend to a thin planar film. In the case of the flexible linear chain surfactant, there is no interaction between the monolayers on the two interfaces in the case of a strong hydrophile-solvent interaction and less coordination for a weaker interaction. In either case, the monolayers remain distinct, as the surfactant only marginally improves wetting.