Flat Solid Substrate Research Articles

Bouncing on thin air: how squeeze forces in the air film during non-wetting droplet bouncing lead to momentum transfer and dissipation

Millimetre-sized droplets are able to bounce multiple times on flat solid substrates irrespective of their wettability, provided that a micrometre-thick air layer is sustained below the droplet, limiting $\mathit{We}$ to ${\lesssim}4$. We study the energy conversion during a bounce series by analysing the droplet motion and its shape (decomposed into eigenmodes). Internal modes are excited during the bounce, yet the viscous dissipation associated with the in-flight oscillations accounts for less than 20 % of the total energy loss. This suggests a significant contribution from the bouncing process itself, despite the continuous presence of a lubricating air film below the droplet. To study the role of this air film we visualize it using reflection interference microscopy. We quantify its thickness (typically a few micrometres) with sub-millisecond time resolution and ${\sim}30~\text{nm}$ height resolution. Our measurements reveal strong asymmetry in the air film shape between the spreading and receding phases of the bouncing process. This asymmetry is crucial for effective momentum reversal of the droplet: lubrication theory shows that the dissipative force is repulsive throughout each bounce, even near lift-off, which leads to a high restitution coefficient. After multiple bounces the droplet eventually hovers on the air film, while continuously experiencing a lift force to sustain its weight. Only after a long time does the droplet finally wet the substrate. The observed bounce mechanism can be described with a single oscillation mode model that successfully captures the asymmetry of the air film evolution.

Nanoparticle Dynamics in a Nanodroplet

We describe the dynamics of 3-10 nm gold nanoparticles encapsulated by ∼30 nm liquid nanodroplets on a flat solid substrate and find that the diffusive motion of these nanoparticles is damped due to strong interactions with the substrate. Such damped dynamics enabled us to obtain time-resolved observations of encapsulated nanoparticles coalescing into larger particles. Techniques described here serve as a platform to study chemical and physical dynamics under highly confined conditions.

The influence of inertia and contact angle on the instability of partially wetting liquid strips: A numerical analysis study

The stability of a thread of fluid deposited on a flat solid substrate is studied numerically by means of the Finite Element Method in combination with an Arbitrary Lagrangian-Eulerian technique. A good agreement is observed when our results are compared with predictions of linear stability analysis obtained by other authors. Moreover, we also analysed the influence of inertia for different contact angles and found that inertia strongly affects the growth rate of the instability when contact angles are large. By contrast, the wave number of the fastest growing mode does not show important variations with inertia. The numerical technique allows us to follow the evolution of the free surface instability until comparatively late stages, where the filament begins to break into droplets. The rupture pattern observed for several cases shows that the number of principal droplets agrees reasonably well with an estimation based on the fastest growing modes.

Opto-Mechanical Scission of Polymer Chains in Photosensitive Diblock-Copolymer Brushes

In this paper we report on an opto-mechanical scission of polymer chains within photosensitive diblock-copolymer brushes grafted to flat solid substrates. We employ surface-initiated polymerization of methylmethacrylate (MMA) and t-butyl methacrylate (tBMA) to grow diblock-copolymer brushes of poly(methylmethacrylate-b-t-butyl methacrylate) following the atom transfer polymerization (ATRP) scheme. After the synthesis, deprotection of the PtBMA block yields poly(methacrylic acid) (PMAA). To render PMMA-b-PMAA copolymers photosensitive, cationic azobenzene containing surfactants are attached to the negatively charged outer PMAA block. During irradiation with an ultraviolet (UV) interference pattern, the extent of photoisomerization of the azobenzene groups varies spatially and results in a topography change of the brush, i.e., formation of surface relief gratings (SRG). The SRG formation is accompanied by local rupturing of the polymer chains in areas from which the polymer material recedes. This opto-mechanically induced scission of the polymer chains takes place at the interfaces of the two blocks and depends strongly on the UV irradiation intensity. Our results indicate that this process may be explained by employing classical continuum fracture mechanics, which might be important for tailoring the phenomenon for applying it to poststructuring of polymer brushes.

A generalized Young’s equation for contact angles of droplets on homogeneous and rough substrates

Using Gibbs’ method of dividing surfaces, the contact angle of a drop on a flat homogeneous rough non-deformable solid substrate is investigated. For this system, a new generalized Young’s equation for the contact angle, including the influences of line tension and which valid for any dividing surface between liquid phase and vapor phase is derived. Under some assumptions, this generalized Young’s equation reduces to the Wenzel’s equation or Rosanov’s equation valid for the surface of tension.

Atomic force microscopy of model lipid membranes

Supported lipid bilayers (SLBs) are biomimetic model systems that are now widely used to address the biophysical and biochemical properties of biological membranes. Two main methods are usually employed to form SLBs: the transfer of two successive monolayers by Langmuir-Blodgett or Langmuir-Schaefer techniques, and the fusion of preformed lipid vesicles. The transfer of lipid films on flat solid substrates offers the possibility to apply a wide range of surface analytical techniques that are very sensitive. Among them, atomic force microscopy (AFM) has opened new opportunities for determining the nanoscale organization of SLBs under physiological conditions. In this review, we first focus on the different protocols generally employed to prepare SLBs. Then, we describe AFM studies on the nanoscale lateral organization and mechanical properties of SLBs. Lastly, we survey recent developments in the AFM monitoring of bilayer alteration, remodeling, or digestion, by incubation with exogenous agents such as drugs, proteins, peptides, and nanoparticles.

Pulsed laser deposition of Mg–Al layered double hydroxide with Ag nanoparticles

Powdered layered double hydroxides (LDHs)—also known as hydrotalcite-like (HT)—compounds have been widely studied due to their applications as catalysts, anionic exchangers or host materials for inorganic or organic molecules. Assembling thin films of nano-sized LDHs onto flat solid substrates is an expanding area of research, with promising applications as sensors, corrosion-resistant coatings, components in optical and magnetic devices. The exploitation of LDHs as vehicles to carry dispersed metal nanoparticles onto a substrate is a new approach to obtain composite thin films with prospects for biomedical and optical applications. We report the deposition of thin films of Ag nanoparticles embedded in a Mg–Al layered double hydroxide matrix by pulsed laser deposition (PLD). The Ag-LDH powder was prepared by co-precipitation at supersaturation and pH = 10 using aqueous solutions of Mg and Al nitrates, Na hydroxide and carbonate, and AgNO3, having atomic ratios of Mg/Al = 3 and Ag/Al = 0.55. The target to be used in laser ablation experiments was a dry pressed pellet obtained from the prepared Ag-LDH powder. Three different wavelengths of a Nd:YAG laser (266, 532 and 1064 nm) working at a repetition rate of 10 Hz were used. X-Ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), and secondary ions mass spectrometry (SIMS) were used to investigate the structure, surface morphology and composition of the deposited films.

Thickness, stability and contact angle of liquid films on and inside nanofibres, nanotubes and nanochannels

While the stability of liquid films on substrates is a classical topic of colloidal science, the availability of nanostructured materials, such as nanotubes, nanofibres and nanochannels, has raised the question of how the stability of liquid films and their wetting behaviour is affected by nanoscale confinement. This paper will present the conditions for the stability of liquid films on and inside cylindrical solid substrates with nanometre scale characteristic dimensions. It is shown that the stability is determined by an effective disjoining/conjoining pressure isotherm which differs from the corresponding disjoining/conjoining pressure isotherm of flat liquid films on flat solid substrates. From the former, the equilibrium contact angles of drops on an outer or inner surface of a cylindrical capillary have been calculated as a function of surface curvature, showing that the expressions for equilibrium contact angles vary for different geometries, in view of the difference in thickness of the film of uniform thickness with which the bulk liquid (drops or menisci) is at equilibrium. These calculations have been extended to the case of glass nanocapillaries and carbon nanotubes, finding good agreement with experimental results in the literature.

Continuous Deposition of a Liquid Thread onto a Moving Substrate. Numerical Analysis and Comparison With Experiments

The printing of a thin line of liquid onto a moving flat solid substrate was studied numerically. For a fixed value of the Capillary number, the window of steady state deposition was explored in terms of the substrate-nozzle gap and flow rate parameter space for two nozzle configurations: a nozzle pointing vertically at the plate and a nozzle slightly tilted towards the substrate motion direction. A lower limit for the flow rate was found, below which no steady state solutions could be obtained. This minimum flow rate increases as the nozzle stand-off and the nozzle tilting do. Solutions near this lower flow rate boundary were stable under a flow rate perturbation. The process was also studied experimentally and the measurements were compared with the corresponding numerical simulations, giving a fairly good agreement, except in the advancing front deposition region.

Statics of polymer droplets on deformable surfaces

The equilibrium properties of polymer droplets on a soft deformable surface are investigated by molecular dynamics simulations of a bead-spring model. The surface consists of a polymer brush with irreversibly end-tethered linear homopolymer chains onto a flat solid substrate. We tune the softness of the surface by varying the grafting density. Droplets are comprised of bead-spring polymers of various chain lengths. First, both systems, brush and polymer liquid, are studied independently in order to determine their static and dynamic properties. In particular, using a numerical implementation of an AFM experiment, we measure the shear modulus of the brush surface and compare the results to theoretical predictions. Then, we study the wetting behavior of polymer droplets with different surface/drop compatibility and on substrates that differ in softness. Density profiles reveal, under certain conditions, the formation of a wetting ridge beneath the three-phase contact line. Cap-shaped droplets and cylindrical droplets are also compared to estimate the effect of the line tension with respect to the droplet size. Finally, the results of the simulations are compared to a phenomenological free-energy calculation that accounts for the surface tensions and the compliance of the soft substrate. Depending on the surface/drop compatibility, surface softness, and drop size, a transition between two regimes is observed: from one where the drop surface energy balances the adhesion with the surface, which is the classical Young-Dupré wetting regime, to another one where a coupling occurs between adhesion, droplet and surface elastic energies.

Straightforward Access to Amphiphilic Dual Bottle Brushes by Combining RAFT, ATRP, and NMP Polymerization in One Sequence

Molecular brush diblock copolymers were synthesized by the orthogonal overlay of the RAFT (reversible addition–fragmentation chain transfer), the ATRP (atom transfer radical polymerization), and the NMP (nitroxide-mediated polymerization) techniques. This unique combination enabled the synthesis of the complex amphiphilic polymers without the need of postpolymerization modifications, using a diblock copolymer intermediate made from two selectively addressable inimers and applying a sequence of four controlled free radical polymerization steps in total. The resulting polymers are composed of a thermosensitive poly(N-isopropylacrylamide) brush as hydrophilic block and a polystyrene brush as hydrophobic block, thus translating the structure of the established amphiphilic diblock copolymers known as macro surfactants to the higher size level of “giant surfactants”. The dual molecular brushes and the aggregates formed on ultra flat solid substrates were visualized by scanning force microscopy (SFM).

Adsorption properties of Mg–Al layered double hydroxides thin films grown by laser based techniques

Powdered layered double hydroxides (LDHs) have been widely studied due to their applications as catalysts, anionic exchangers or host materials for inorganic and/or organic molecules. Assembling nano-sized LDHs onto flat solid substrates forming thin films is an expanding area of research due to the prospects of novel applications as sensors, corrosion-resistant coatings, components in optical and magnetic devices.Continuous and adherent thin films were grown by laser techniques (pulsed laser deposition – PLD and matrix assisted pulsed laser evaporation – MAPLE) starting from targets of Mg–Al LDHs. The capacity of the grown thin films to retain a metal (Ni) from contaminated water has been also explored. The thin films were immersed in an Ni(NO3)2 aqueous solutions with Ni concentrations of 10−3% (w/w) (1g/L) and 10−4% (w/w) (0.1g/L), respectively. X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) combined with energy dispersive X-ray analysis (EDX) were the techniques used to characterize the prepared materials.

Monolayer Characterization of Amphiphilic Hexa-peri-hexabenzocoronene Derivatives

Monolayer properties and structures of two amphiphilic derivatives of hexa-peri-hexabenzocoronene (HBC) have been investigated at the air/water interface and on solid supports. The derivatives possess two dodecyl chains directly linked to one side of the HBC moiety, and two triethylene glycol (TEG) monomethyl ether chains coupled to the other side through single paraphenylene (Ph) or acetylene (Ac) group. The compounds with Ph and Ac are abbreviated as Ph-TEG and Ac-TEG, respectively. Both compounds formed stable Langmuir monolayers on the water surface when spread from dilute chloroform solutions. Brewster angle microscopic observation implied that two-dimensional solid-phase islands were spontaneously formed after spreading, and gathered upon lateral compression. Structural investigation was performed for the monolayers deposited on flat solid substrates by several techniques of surface analysis. A significant difference was found in the degree of tilt of the HBC cores in the monolayers by X-ray reflectometry: the core of Ac-TEG is more tilted toward the substrate surface than that of Ph-TEG.

The friction of a mesh-like super-hydrophobic surface

When a liquid droplet is located above a super-hydrophobic surface, it only barely touches the solid portion of the surface, and therefore slides very easily on it. More generally, super-hydrophobic surfaces have been shown to lead to significant reduction in viscous friction in the laminar regime, so it is of interest to quantify their effective slipping properties as a function of their geometric characteristics. Most previous studies considered flows bounded by arrays of either long grooves, or isolated solid pillars on an otherwise flat solid substrate, and for which therefore the surrounding air constitutes the continuous phase. Here we consider instead the case where the super-hydrophobic surface is made of isolated holes in an otherwise continuous no-slip surface, and specifically focus on the mesh-like geometry recently achieved experimentally. We present an analytical method to calculate the friction of such a surface in the case where the mesh is thin. The results for the effective slip length of the surface are computed, compared to simple estimates, and a practical fit is proposed displaying a logarithmic dependence on the area fraction of the solid surface.

Formation of surface-grafted polymeric amphiphilic coatings comprising ethylene glycol and fluorinated groups and their response to protein adsorption

Amphiphilic polymer coatings were prepared by first generating surface-anchored polymer layers of poly(2-hydroxyethyl methacrylate) (PHEMA) on top of flat solid substrates followed by postpolymerization reaction on the hydroxyl terminus of HEMA's pendent group using three classes of fluorinating agents, including organosilanes, acylchlorides, and trifluoroacetic anhydride (TFAA). The distribution of the fluorinated groups inside the polymer brushes was assessed by means of a suite of analytical probes, including contact angle, ellipsometry, infrared spectroscopy, atomic force microscopy, and near-edge x-ray absorption fine structure spectroscopy. While organosilane modifiers were found to reside primarily close to the tip of the brush, acylchlorides penetrated deep inside PHEMA thus forming random copolymers P(HEMA-co-fHEMA). The reaction of TFAA with the PHEMA brush led to the formation of amphiphilic diblocks, PHEMA-b-P(HEMA-co-fHEMA), whose bottom block comprised unmodified PHEMA and the top block was made of P(HEMA-co-fHEMA) rich in the fluorinated segments. This distribution of the fluorinated groups endowed PHEMA-b-P(HEMA-co-fHEMA) with responsive properties; while in hydrophobic environment P(HEMA-co-fHEMA) segregated to the surface, when in contact with a hydrophilic medium, PHEMA partitioned at the brush surface. The surface activity of the amphiphilic coatings was tested by studying the adsorption of fibrinogen (FIB). While some FIB adsorption occurred on most coatings, the ones made by TFAA modification of PHEMA remained relatively free of FIB.

Tuning Gold Nanoparticle−Poly(2-hydroxyethyl methacrylate) Brush Interactions: From Reversible Swelling to Capture and Release

Tailoring the interaction between surfaces and nanoparticles (NPs) affords great opportunities for a range of applications, including sensors, information storage, medical diagnostics, and filtration membranes. In addition to controlling local ordering and microscale patterning of the NPs, manipulating the temporal factors determining the strength of the interaction between NP and surface enables dynamic modulation of these structural characteristics. In this contribution we demonstrate robust polymer brush-NP hybrids that exhibit both reversible swelling and reversible NP adsorption/desorption. Polymer brush functionality is tailored through post-functionalization of poly(2-hydroxyethyl methacrylate) (PHEMA) brushes on flat solid substrates with alpha-amine conjugates ranging from perfluoro alkanes to poly(ethylene glycol) of varying molecular weights. The type of functionality controls NP affinity for the surfaces. In the case of poly(ethylene glycol) (PEG), the molecular weight (MW) of the PEG dictates adsorption and desorption phenomena. Higher MW PEG chains possess increased binding affinity toward NPs, which leads to higher relative Au-NP densities on the PHEMA-g-PEG brushes and concurrent sluggish desorption of NPs by thermal stimulus. Adsorption and desorption phenomena are further modulated by NP size yielding a system where adsorption and desorption are controlled by a delicate balance between the competitive energetics of polymer brush chelation versus solvation.

Weakly bound buffer layers: A versatile template for metallic nano-clusters growth and film patterning on solid surfaces

Buffer layers composed of weakly bound atoms or molecules on solid surfaces are discussed as a versatile platform for size controlled growth of nano-clusters and for patterning of thin metallic films. Metallic nano-crystals can be prepared and their size and density be controlled by varying the film thickness. Cold metallic or oxide clusters, softly land and deposit on solid substrates via the Buffer Layer Assisted Growth (BLAG) method. Their final structure, therefore, reflects purely the interaction with the substrate with no kinetic constraints that may play a role in direct deposition methods of hot atoms. The nature of the buffer film, being a rare gas or a molecular film, can somewhat affect the shape of clusters as well. Applying laser ablation techniques, these weakly bound films were demonstrated to assist in patterning of metallic films. It operates on practically any cold, flat solid substrate that absorbs the laser light. Parallel stripes at sub-micron width, millimeter long, were obtained experimentally, with line width determined by the ablating laser power. The versatility of these weakly bound films in manipulating the structure of metallic particles and thin films is discussed in its wider potential scope.

An Analytical Model to Describe the Efficiency of an Immersion Rinsing Process

In this paper, a simple model is presented, describing an immersion rinsing process for flat solid substrates (e.g., semiconductor wafers). It is assumed that together with the solid a layer of processing liquid is transferred into a tank filled with rinsing liquid. The model calculates the replacement of the processing liquid with rinsing liquid as a function of the rinse time and the position in the tank. For static rinsing systems an analytical expression is readily obtained. For dynamic systems (where liquid convection plays a role) the concept of a convective boundary layer is introduced. It is assumed that within this boundary layer diffusion is the dominant transport mechanism while outside the boundary layer convection is dominant. Under these assumptions an analytical expression can also be obtained for dynamic rinsing with the thickness of the convective boundary layer as a process parameter. The resulting analytical expressions can be readily used to calculate the concentration of remaining processing liquid in the vicinity of the solid substrate as a function of rinse time. This provides a good way to determine the efficiency of the rinsing process. Moreover, these expressions allow us to assess the effect of changes in boundary layer thickness and thus can help with the optimization of existing rinsing processes.

Formation and properties of multivariant assemblies of surface-tethered diblock and triblock copolymers

We present methodologies for fabricating block copolymer assemblies grafted onto flat solid substrates, where each block of the copolymer possesses a systematic and gradual variation of molecular weight as a function of the position on the substrate. We demonstrate the utility of this technique on two case studies. In the first project, we generate surface-tethered poly[(2-hydroxyethyl methacrylate)-b-(methyl methacrylate)] (PHEMA-b-PMMA) diblock copolymer brushes and study systematically morphological transitions associated with collapsing either the top PMMA or the bottom PHEMA block while keeping the other block solvated. Scanning force microscopy studies of systems having the top block collapsed reveal the presence of either flat (F), or micellar (M) or bicontinuous (BC) morphologies, whose locus in the phase diagram agrees with theoretical predictions and results of computer simulations. The second case study demonstrates the extension of the deposition method to the case of surface-anchored triblock copolymer brushes. Specifically, we present results pertaining to the formation of poly[(2-hydroxyethyl methacrylate)-b-(methyl methacrylate)-b-(dimethylaminoethyl methacrylate)] brushes with independent variation of all three block lengths.

Effect of Solvent Quality and Chain Confinement on the Kinetics of Polystyrene Bromination

We report on the kinetics of the bromination of free polystyrene (PS) chains in bulk solution and those anchored on flat solid substrates by performing the bromination reaction in different solvents, including nitrobenzene (NB), 1-chlorodecane (CD), 1-chloroundecane (CUD), and 1-chlorododecane (CDD), at various temperatures. We find that bulk bromination of PS follows the second-order kinetic in bromine and the reaction rate increases with increasing dielectric constant of the solvent (ε). In spite of εCDD > εCD, the bulk bromination kinetics of PS in CDD is slower than that in CD because of lower solubility of PS in CDD than in CD. In addition, we demonstrate that the reaction rates for brominating PS brushes anchored to flat solid substrates are much slower than those for brominating free PS chains in bulk solution. We attribute this behavior to steric hindrance due to PS confinement on the substrate.