Hole-initiated melting process of thin films.

We perform numerical and experimental studies on the melting process of thin films initiated by a small hole in the continuum regime. The presence of a nontrivial capillary surface, namely the liquid/air interface, leads to a few counterintuitive results: (1) The melting point is elevated if the film surface is partially wettable, even with a small contact angle. (2) For a film that is finite in size, melting may prefer to start from the outer boundary rather than a hole inside. (3) More complex melting scenarios may arise, including morphology transitions and the "de facto" melting point being a range instead of a single value. These are verified by experiments on melting alkane films between silica and air. This work continues a series of investigations on the capillary aspects of melting. Both our model and analysis approach can be easily generalized to other systems.

Diphenylalanine Deposition by Dip-Coating from Acidic Solutions: Fibers and Closed Homogeneous Films.

A simple but precisely controllable strategy by molecular assembly that enables the construction of biomaterials is always in the development. Dip-coating deposition of diphenylalanine (FF) onto planar solid substrates from aqueous acidic (acetic, propanoic, formic, and HCl) solutions is studied as a function of the process control parameters (deposition speed, initial concentration of FF and acids, and external gas flow). The results are studied by optical microscopy, AFM, and ellipsometry. For low acidity and low FF concentrations, FF forms microfibers, nanofibers, or stripes of fiber aggregates. For higher acidity and FF concentrations, closed films of FF of remarkably smooth surfaces are found. The thickness of these films can be well-controlled by the FF concentration and the deposition speed and explained by the evaporation regime. These unusual results provide new possibilities to fabricate more abundant structures by a simple strategy and develop a candidate for biological membrane areas.

Controlled-Alignment Patterns of Dipeptide Micro- and Nanofibers.

Ordered assemblies of the peptide diphenylalanine (FF) are produced and deposited on planar substrates. The FF aggregate growth is achieved through precipitation from aqueous ammonia solutions induced by solvent evaporation. The applied dip-coating technique confines the FF assembly growth to a narrow zone near the three-phase contact. The growth was observed online by optical microscopy and was investigated systematically as a function of the process parameters. Depending on the external gas flow (to influence solvent evaporation), the withdrawal speed, the initial FF, and the initial ammonia concentrations, FF forms long, straight, and rigid microfibers and/or shorter, curved nanofibers. Under certain process conditions, the FF fibers can also aggregate into stripes. These can be deposited as large arrays of uniform stripes with regular widths and spacings. Scenarios leading to the various types of fibers and the stripe formation are presented and discussed in view of the experimental findings.

Controlled Deposition of Nanosize and Microsize Particles by Spin-Casting.

The deposition of nanosize and microsize spherical particles on planar solid substrates by hydrodynamic-evaporative spin-casting is studied. The particles are dispersed in a volatile liquid, which evaporates during the process, and the particles are finally deposited on the substrate. Their coverage, Γ, depends on the processing parameters (concentration by weight, particles size, etc.). The behavior of the particles during the spin-casting process and their final Γ values are investigated. It is found that for up to particle diameters of a few micrometers, particle deposition can be described by a theoretical approach developed for the spin-casting of polymer solutions (Karpitschka, S.; Weber, C. M.; Riegler, H. Chem. Eng. Sci. 2015, 129, 243-248. Danglad-Flores, J.; Eickelmann, S.; Riegler, H. Chem. Eng. Sci. 2018, 179, 257-264). For large particles, this basic theory fails. The causes of this failure are analyzed, and a corrected, more general theoretical approach is presented. It takes into account particle size effects as well as particle sedimentation. In summary, we present new insights into the spin-cast process of particle dispersions, analyze the contributions affecting the final particle coverage, and present a theoretical approach which describes and explains the experimental findings.

Meniscus Shape around Nanoparticles Embedded in Molecularly Thin Liquid Films.

Individual nanoparticles embedded in molecularly thin films at planar substrates and the resulting film surface distortion (meniscus) adjacent to the nanoparticles are investigated by conventional optical reflection microscopy. Even for nanoparticles much smaller than the Rayleigh diffraction limit, the meniscus creates such a pronounced optical footprint that the location of the nanoparticles can be identified. This is because the decay length (lateral extension) of the meniscus exceeds the size of the nanoparticle by orders of magnitude. Therefore, for the first time, the exact shape of the meniscus of the liquid adjacent to a nanosize object could be measured and analyzed. The meniscus has a zero curvature shape (cosine hyperbolic). The liquid in the meniscus is in pressure equilibrium with the far-field planar film. The decay length decreases with the decreasing nanoparticle size. However, it is independent of the far-field film thickness. Supposedly, the decay length is determined by van der Waals interactions although it is unknown what determines its (unexpectedly large) absolute value. The presented technical approach may be used to investigate biological systems (for instance, surface distortions in supported membranes caused by proteins or protein aggregates).

Controlling Indomethacin Release through Vapor-Phase Deposited Hydrogel Films by Adjusting the Cross-linker Density.

Vapor-phase deposited polymer coatings are applied on thin indomethacin films to modify the drug release. Hydrogel-forming co-polymers of 2-hydroxyethyl methacrylate and ethylene glycol dimethacrylate were prepared directly on top of solution cast indomethacin thin films by initiated Chemical Vapor Deposition (iCVD). This technique allows for solvent-free processing under mild conditions, thus minimizing a potential impact on the pharmaceutical. The drug release behavior, among other properties, was evaluated for polymers of different compositions and at different temperatures. The data show that the release kinetics can be tuned by several orders of magnitude as the cross-linker fraction is varied in the polymer coating. While uncoated indomethacin films were fully released within an hour, polymer coatings showed gradual liberation over several hours to days. Additional insight is gained from evaluating the experimental dissolution data in the framework of diffusive transport. The results of this study show that the iCVD technique has some promises for pharmaceutical technology, potentially allowing for tailored release behavior also for other drug systems.

Rupture of ultrathin solution films on planar solid substrates induced by solute crystallization.

On-line optical imaging of continuously thinning planar films in a spin cast configuration reveals the rupture behavior of ultra-thin films of binary mixtures of a volatile solvent and a nonvolatile solute. The pure solvents completely wet the silica substrates whereas the solution films rupture at certain film thicknesses, hrupture, which depend on, c0, the initial weighing in solute concentrations. With small c0, hrupture increases proportional to c0. With high c0, all films rupture at hrupture≈50nm, independent of c0. The findings can be explained by the solute enrichment during the evaporative thinning. Solute crystallization at the liquid/substrate interface upon reaching solute supersaturation leads to locally different wetting properties. This induces locally the rupture of the film as soon as it is sufficiently thin. A proper data rescaling based on this scenario yields a universal rupture behavior of various different solvent/solute mixtures.

Directed Self-Assembly of Dipeptide Single Crystal in a Capillary.

Controlled growth of one-dimensional nanostructures is playing a key role in creating types of materials for functional devices. Here, we report procedures for controlled assembly of the dipeptide diphenylalanine (FF) into aligned and ultralong single crystals in a capillary. With the evaporation of solvent, nucleation of the crystal occurred in the confined region, and the crystal grew continuously with a supply of molecules from the concentration gradient system inside the capillary. Based on the "Knudsen regime", an ultralong aligned individual FF single crystal possessing an active optical waveguide property at macroscopic length scale could be obtained. Moreover, capillary is also an effective microdevice to investigate the disassembly process of the FF single crystals. This strategy has potentials to broaden the range of applications of aligned organic nanomaterials.

Capillary-Enhanced Immobilization of Nanoparticles.

The contact between a spherical nanoparticle and a planar substrate is surrounded by an annular wedge cavity. In adsorption processes, this acts like a small pore. Interfacial/capillarity effects lead to an accumulation of adsorbate in this region ("capillary condensation"). This effectively increases the contact area between the particles and the substrate. Thus, capillary-enhanced adsorbate accumulation increases the adhesion between the nanoparticles and the planar surface, which effectively immobilizes the particles.

Solvent Vapor Annealing of Amorphous Carbamazepine Films for Fast Polymorph Screening and Dissolution Alteration.

Solubility enhancement and thus higher bioavailability are of great importance and a constant challenge in pharmaceutical research whereby polymorph screening and selection is one of the most important tasks. A very promising approach for polymorph screening is solvent vapor annealing where a sample is exposed to an atmosphere saturated with molecules of a specific chemical/solvent. In this work, amorphous carbamazepine thin films were prepared by spin coating, and the transformation into crystalline forms under exposure to solvent vapors was investigated. Employing grazing incidence X-ray diffraction, four distinct carbamazepine polymorphs, a solvate, and hydrates could be identified, while optical microscopy showed mainly spherulitic morphologies. In vitro dissolution experiments revealed different carbamazepine release from the various thin-film samples containing distinct polymorphic compositions: heat treatment of amorphous samples at 80 °C results in an immediate release; samples exposed to EtOH vapors show a drug release about 5 times slower than this immediate one; and all the others had intermediate release profiles. Noteworthy, even the sample of slowest release has a manifold faster release compared to a standard powder sample demonstrating the capabilities of thin-film preparation for faster drug release in general. Despite the small number of samples in this screening experiment, the results clearly show how solvent vapor annealing can assist in identifying potential polymorphs and allows for estimating their impact on properties like bioavailability.

Self-Assembly of Ultralong Aligned Dipeptide Single Crystals.

Oriented arrangement of single crystals plays a key role in improving the performance of their functional devices. Herein we describe a method for the exceptionally fast fabrication (mm/min) of ultralong aligned dipeptide single crystals (several centimeters). It combines an induced nucleation step with a continuous withdrawal of substrate, leading to specific evaporation/composition conditions at a three-phase contact line, which makes the growth process controllable. These aligned dipeptide fibers possess a uniform cross section with active optical waveguiding properties that can be used as waveguiding materials. The approach provides guidance for the controlled arrangement of organic single crystals, a family of materials with considerable potential applications in large-scale functional devices.

Marangoni Contraction of Evaporating Sessile Droplets of Binary Mixtures.

The Marangoni contraction of sessile drops of a binary mixture of a volatile and a nonvolatile liquid has been investigated experimentally and theoretically. The origin of the contraction is the locally inhomogeneous evaporation rate of sessile drops. This leads to surface tension gradients and thus to a Marangoni flow. Simulations show that the interplay of Marangoni flow, capillary flow, diffusive transport, and evaporative losses can establish a quasistationary drop profile with an apparent nonzero contact angle even if both liquid components individually wet the substrate completely. Experiments with different solvents, initial mass fractions, and gaseous environments reveal a previously unknown universal power-law relation between the apparent contact angle and the relative undersaturation of the ambient atmosphere: θapp ∼ (RHeq - RH)1/3. This experimentally observed power law is in quantitative agreement with simulation results. The exponent can also be inferred from a scaling analysis of the hydrodynamic-evaporative evolution equations of a binary mixture of liquids with different volatilities.

Thermally driven smoothening of molecular thin films: Structural transitions in n-alkane layers studied in real-time.

We use thermal annealing to improve smoothness and to increase the lateral size of crystalline islands of n-tetratetracontane (TTC, C44H90) films. With in situ x-ray diffraction, we find an optimum temperature range leading to improved texture and crystallinity while avoiding an irreversible phase transition that reduces crystallinity again. We employ real-time optical phase contrast microscopy with sub-nm height resolution to track the diffusion of TTC across monomolecular step edges which causes the unusual smoothing of a molecular thin film during annealing. We show that the lateral island sizes increase by more than one order of magnitude from 0.5 µm to 10 µm. This desirable behavior of 2d-Ostwald ripening and smoothing is in contrast to many other organic molecular films where annealing leads to dewetting, roughening, and a pronounced 3d morphology. We rationalize the smoothing behavior with the highly anisotropic attachment energies and low surface energies for TTC. The results are technically relevant for the use of TTC as passivation layer and as gate dielectric in organic field effect transistors.

Periodic Precipitation Patterns during Coalescence of Reacting Sessile Droplets.

The coalescence behavior of two sessile drops that contain different chemical reactants (cerium nitrate and oxalic acid) and its impact on the formation of the solid precipitate (cerium oxalate) are investigated. With different liquids, the surface tension difference in the moment of drop-drop contact can induce a Marangoni flow. This flow can strongly influence the drop-drop coalescence behavior and thus, with reacting liquids, also the reaction and its products (through the liquid mixing). In our study we find three distinctly different coalescence behaviors ("barrier", "intermediate", "noncoalescence"), in contrast to only two behaviors that were observed in the case of nonreacting liquids. The amount of liquid mixing and thus the precipitation rate are very different for the three cases. The "intermediate" case, which exhibits the strongest mixing, has been studied in more detail. For high oxalic acid concentrations, mainly needle-like aggregates, and for low concentrations, mainly flower-like precipitate morphologies are obtained. In a transition range of the oxalic acid concentration, both morphologies can be produced. With the applied coalescence conditions, the different aggregate particles are arranged and fixed in a precipitate raft in a regular, periodic line pattern. This confirms the drop-drop coalescence configuration as a convection-reaction-diffusion system, which can have stationary as well as oscillatory behavior depending on the system parameters.

The evaporation behavior of sessile droplets from aqueous saline solutions.

Quantitative experiments on the evaporation from sessile droplets of aqueous saline (NaCl) solutions show a strong dependence on salt concentration and droplet shape. The experiments were performed with seven decades of initial NaCl concentrations, with various droplet sizes and with different contact angles. The evaporation rate is significantly lower for high salt concentrations and small contact angles than what is expected from the well-accepted diffusion-controlled evaporation scenario for sessile droplets, even if the change of the vapor pressure due to the salt is taken into account. Particle tracking velocimetry reveals that this modification of the evaporation behavior is caused by marangoni flows that are induced by surface tension gradients originating from the local evaporative peripheral salt enrichment. In addition it is found that already very low salt concentrations lead to a pinning of the three phase contact line. Whereas droplets with concentration ≥10(-6) M NaCl are pinned as soon as evaporation starts, droplets with lower salt concentration do evaporate in a constant contact angle mode. Aside from new, fundamental insights the findings are also relevant for a better understanding of the widespread phenomenon of corrosion initiated by sessile droplets.

Coalescence and noncoalescence of sessile drops: impact of surface forces.

Due to capillarity, sessile droplets of identical liquids will instantaneously fuse when they come in contact at their three-phase lines. However, with drops of different, completely miscible liquids, instantaneous coalescence can be suppressed. Instead, the drops remain in a state of noncoalescence for some time, with the two drop bodies connected only by a thin neck. The reason for this noncoalescence is the surface tension difference, Δγ, between the liquids. If Δγ is sufficiently large, then it induces a sufficiently strong Marangoni flow, which keeps the main drop bodies temporarily separated. Studies with spreading drops have revealed that the boundary between instantaneous coalescence and noncoalescence is sharp (Karpitschka, S.; Riegler, H. J. Fluid. Mech. 2014, 743, R1). The boundary is a function of two parameters only: Δγ and Θ(a), the arithmetic mean of the contact angles in the moment of drop-drop contact. It appears plausible that surface forces (the disjoining pressure) could also influence the coalescence behavior. However, in experiments with spreading drops, surface forces always promote coalescence and their influence might be obscured. Therefore, we present here coalescence experiments with partially wetting liquids and compare the results to the spreading case. We adjust different equilibrium contact angles (i.e., different surface forces) with different substrate surface coatings. As for spreading drops, we observe a sharp boundary between regimes of coalescence and noncoalescence. The boundary follows the same power law relation for both partially and completely wetting cases. Therefore, we conclude that surface forces have no significant, explicit influence on the coalescence behavior of sessile drops from different miscible liquids.

Nonintrusive optical visualization of surface nanobubbles.

Individual surface nanobubbles are visualized with nonintrusive optical interference-enhanced reflection microscopy, demonstrating that their formation is not a consequence of the hitherto used intrusive atomic force microscopy technique. We then use this new and fast technique to demonstrate that surface nanobubbles form in less than a few seconds after ethanol-water exchange, which is the standard procedure for their preparation, and examine how they react to temperature variations.

Noncoalescence of sessile drops from different but miscible liquids: hydrodynamic analysis of the twin drop contour as a self-stabilizing traveling wave.

Capillarity always favors drop fusion. Nevertheless, sessile drops from different but completely miscible liquids often do not fuse instantaneously upon contact. Rather, intermediate noncoalescence is observed. Two separate drop bodies, connected by a thin liquid neck, move over the substrate. Supported by new experimental data, a thin film hydrodynamic analysis of this state is presented. Presumably advective and diffusive volume fluxes in the neck region establish a localized and temporarily stable surface tension gradient. This induces a local surface (Marangoni) flow that stabilizes a traveling wave, i.e., the observed moving twin drop configuration. The theoretical predictions are in excellent agreement with the experimental findings.

Impact of negative line tension on the shape of nanometer-size sessile droplets.

The sign and value of the line tension has been measured from the size dependence of the contact angle of nanometer-size sessile fullerene (C60) droplets on the planar SiO2 interface, measured with atomic force microscopy (AFM). Analysis according to the modified Young's equation indicates a negative line tension, with a magnitude between -10{-11} and -10{-10} N/m, in good agreement with theoretical predictions. The experiments also indicate that droplets with contact area radii below 10 nm are in fact two-dimensional round terraces.

Quantitative experimental study on the transition between fast and delayed coalescence of sessile droplets with different but completely miscible liquids.

Quantitative experimental data on the coalescence behavior of sessile droplets with different but completely miscible liquids are presented. The liquids consist of various aqueous mixtures of different nonvolatile diols and carbon acids with surface tensions ranging from 33 to 68 mN/m, contact angles between 9 degrees and 20 degrees, and viscosities from 1 to 12 cP. Two distinctly different coalescence behaviors, a delayed and a fast regime, are found. The transition between the two behaviors is remarkably sharp. It is found that the coalescence mode depends predominantly on the differences in the surface tensions of the two droplets. If the surface tension difference exceeds approximately 3 mN/m, the coalescence is delayed. If it is less, droplet fusion occurs fast. Within the investigated parameter space, the transition seems independent from droplet size, absolute values of the surface tensions, and viscosity. Certain aspects of the experimental findings are explained with the simple hydrodynamic model presented in a recent publication.