Multiple Wetting-Dewetting States of a Water Droplet on Dual-Scale Hierarchical Structured Surfaces.

Surfaces with microscale roughness can entail dual-scale hierarchical structures such as the recently reported nano/microstructured surfaces produced in the laboratory (Wang et al. Nature2020, 582, 55-57). However, how the dual-scale hierarchical structured surface affects the apparent wetting/dewetting states of a water droplet, and the transitions between the states are still largely unexplored. Here, we report a systematic large-scale molecular dynamics (MD) simulation study on the wetting/dewetting states of water droplets on various dual-scale nano/near-submicrometer structured surfaces. To this end, we devise slab-water/slab-substrate model systems with a variety of dual-scale surface structures and with different degrees of intrinsic wettability (as measured based on the counterpart smooth surface). The dual-scale hierarchical structure can be described as "nanotexture-on-near-submicrometer-hill". Depending on three prototypical nanotextures, our MD simulations reveal five possible wetting/dewetting states for a water droplet: (i) Cassie state; (ii) infiltrated upper-valley state; (iii) immersed nanotexture-on-hill state; (iv) infiltrated valley state; and (v) Wenzel state. The transitions between these wetting/dewetting states are strongly dependent on the intrinsic wettability (E in), the initial location of the water droplet, the height of the nanotextures (H 1), and the spacing between nanotextures (W 1). Notably, E in-H 1 and E in-W 1 diagrams show that regions of rich wetting/dewetting states can be identified, including regions where between one to five states can coexist.

Turning a Superhydrophilic Surface Weakly Hydrophilic: Topological Wetting States.

For water droplets placed on a rough or structured surface, two distinct wetting states commonly observed are either the Wenzel state (droplets wet the surface without showing air pockets beneath the droplets) or the Cassie state (droplets reside on top of the structure with air pockets trapped beneath the droplets). Herein, we show molecular dynamics (MD) simulation evidence of a previously unreported wetting behavior, i.e., the rise of multiple Wenzel states on the structured surfaces whose flat-surface counterparts are superhydrophilic (i.e., complete wetting surfaces with the hallmark of zero contact angle for water droplets). Specifically, our MD simulations show that on the structured surfaces with topology of closed-loop nanowalls/nanochannels, the water droplet can exhibit multiple Wenzel wetting states with the apparent contact angles >0°. We name these distinct multiple Wenzel states as "topological wetting states" because their existence can be attributed to the topology of the closed-loop nanowalls/nanochannels. Regardless of the shape of the closed loops, such topological wetting states can always arise due to the topological invariant (i.e., all closed loops entail the same topological genus value). This unusual wetting behavior is contrary to the conventional view (and to the prediction of the Wenzel equation), namely, a rough hydrophilic surface should have stronger hydrophilicity than its flat-surface counterpart.

Effects of Femtosecond Laser Surface Processed Nanoparticle Layers on Pool Boiling Heat Transfer Performance.

An experimental investigation of the effects of layers of nanoparticles formed during femtosecond laser surface processing (FLSP) on pool boiling heat transfer performance has been conducted. Five different stainless steel 304 samples with slightly different surface features were fabricated through FLSP, and pool boiling heat transfer experiments were carried out to study the heat transfer characteristics of each surface. The experiments showed that the layer(s) of nanoparticles developed during the FLSP processes, which overlay FLSP self-organized microstructures, can either improve or degrade boiling heat transfer coefficients (HTC) depending on the overall thickness of the layer(s). This nanoparticle layer thickness is an indirect result of the type of microstructure created. The HTCs were found to decrease with increasing nanoparticle layer thickness. This trend has been attributed to added thermal resistance. Using a focused ion beam milling process and transmission electron microscopy (TEM), the physical and chemical properties of the nanoparticle layers were characterized and used to explain the observed heat transfer results. Results suggest that there is an optimal nanoparticle layer thickness and material composition such that both the HTCs and critical heat flux (CHF) are enhanced.

Investigation of femtosecond laser induced ripple formation on copper for varying incident angle.

The hydrodynamic mechanisms associated with the formation of femtosecond laser induced ripples on copper for two angles of incidence are reported. Laser pulse length used for this work is 35 fs. A revised two-temperature model is presented that comprises transient changes of optical characteristics during the irradiation with femtosecond pulses to model relaxation processes and thermal response in bulk copper. The theoretical model takes into account the fluid flow dynamics that result in ripple periods shorter than the wavelength of the surface plasmon polaritons. Theoretical and experimental results are reported for incident angles of 0° and 45° relative to the surface normal. There is agreement between the experimentally measured and the theoretically predicted ripple periodicity for 50 pulses at 0° incidence. By contrast, for 100 pulses at 0° incidence, and 50 and 100 pulses at 45° incidence, the experimentally measured ripples have a larger period than the one predicted by the model while the trends in period with increased incident angle, and increased fluence are in agreement between the experimental and the theoretical results.

Growth mechanisms of multiscale, mound-like surface structures on titanium by femtosecond laser processing.

Femtosecond laser surface processing (FLSP) can be used to functionalize many surfaces, imparting specialized properties such as increased broadband optical absorption or super-hydrophobicity/-hydrophilicity. In this study, the subsurface microstructure of a series of mound-like FLSP structures formed on commercially pure titanium using five combinations of laser fluence and cumulative pulse counts was studied. Using a dual beam Scanning Electron Microscope with a Focused Ion Beam, the subsurface microstructure for each FLSP structure type was revealed by cross-sectioning. The microstructure of the mounds formed using the lowest fluence value consists of the original Ti grains. This is evidence that preferential laser ablation is the primary formation mechanism. However, the underlying microstructure of mounds produced using higher fluence values was composed of a distinct smaller-grained α-Ti region adjacent to the original larger Ti grains remaining deeper beneath the surface. This layer was attributed to resolidification of molten Ti from the hydrodynamic Marangoni effect driven fluid flow of molten Ti, which is the result of the femtosecond pulse interaction with the material.

Micro/nanostructures formation by femtosecond laser surface processing on amorphous and polycrystalline Ni60Nb40.

Femtosecond laser surface processing is a technology that can be used to functionalize many surfaces, imparting specialized properties such as increased broadband optical absorption or superhydrophilicity/superhydrophobicity. In this study, two unique classes of surface structures, below surface growth (BSG) and above surface growth (ASG) mounds, were formed by femtosecond laser surface processing on amorphous and polycrystalline Ni60Nb40 with two different grain sizes. Cross sectional imaging of these mounds revealed thermal evidence of the unique formation processes for each class of surface structure. BSG mounds formed on all three substrates using the same laser parameters had similar surface morphology. The microstructures in the mounds were unaltered compared with the substrate before laser processing, suggesting their formation was dominated by preferential valley ablation. ASG mounds had similar morphology when formed on the polycrystalline Ni60Nb40 substrates with 100 nm and 2 [H9262]m grain size. However, the ASG mounds had significantly wider diameter and higher peak-to-valley heights when the substrate was amorphous Ni60Nb40. Hydrodynamic melting was primarily responsible for ASG mound formation. On amorphous Ni60Nb40 substrates, the ASG mounds are most likely larger due to lower thermal diffusivity. There was clear difference in growth mechanism of femtosecond laser processed BSG and ASG mounds, and grain size does not appear to be a factor.

Formation of aggregated nanoparticle spheres through femtosecond laser surface processing.

A detailed structural and chemical analysis of a class of self-organized surface structures, termed aggregated nanoparticle spheres (AN-spheres), created using femtosecond laser surface processing (FLSP) on silicon, silicon carbide, and aluminum is reported in this paper. AN-spheres are spherical microstructures that are 20-100 µm in diameter and are composed entirely of nanoparticles produced during femtosecond laser ablation of material. AN-spheres have an onion-like layered morphology resulting from the build-up of nanoparticle layers over multiple passes of the laser beam. The material properties and chemical composition of the AN-spheres are presented in this paper based on scanning electron microscopy (SEM), focused ion beam (FIB) milling, transmission electron microscopy (TEM), and energy dispersive x-ray spectroscopy (EDX) analysis. There is a distinct difference in the density of nanoparticles between concentric rings of the onion-like morphology of the AN-sphere. Layers of high-density form when the laser sinters nanoparticles together and low-density layers form when nanoparticles redeposit while the laser ablates areas surrounding the AN-sphere. The dynamic nature of femtosecond laser ablation creates a variety of nanoparticles that make-up the AN-spheres including Si/C core-shell, nanoparticles that directly fragmented from the base material, nanoparticles with carbon shells that retarded oxidation, and amorphous, fully oxidized nanoparticles.

Experimental explanation of the formation mechanism of surface mound-structures by femtosecond laser on polycrystalline Ni60Nb40.

Femtosecond laser surface processing (FLSP) is an emerging technique for creating functionalized surfaces with specialized properties, such as broadband optical absorption or superhydrophobicity/superhydrophilicity. It has been demonstrated in the past that FLSP can be used to form two distinct classes of mound-like, self-organized micro/nanostructures on the surfaces of various metals. Here, the formation mechanisms of below surface growth (BSG) and above surface growth (ASG) mounds on polycrystalline Ni60Nb40 are studied. Cross-sectional imaging of these mounds by focused ion beam milling and subsequent scanning electron microscopy revealed evidence of the unique formation processes for each class of microstructure. BSG-mound formation during FLSP did not alter the microstructure of the base material, indicating preferential valley ablation as the primary formation mechanism. For ASG-mounds, the microstructure at the peaks of the mounds was clearly different from the base material. Transmission electron microscopy revealed that hydrodynamic melting of the surface occurred during FLSP under ASG-mound forming conditions. Thus, there is a clear difference in the formation mechanisms of ASG- and BSG-mounds during FLSP.

Self­propelled droplets on heated surfaces with angled self­assembled micro/nanostructures.

Directional and ratchet-like functionalized surfaces can induce liquid transport without the use of an external force. In this paper, we investigate the motion of liquid droplets near the Leidenfrost temperature on functionalized self-assembled asymmetric microstructured surfaces. The surfaces, which have angled microstructures, display unidirectional properties. The surfaces are fabricated on stainless steel through the use of a femtosecond laser-assisted process. Through this process, mound-like microstructures are formed through a combination of material ablation, fluid flow, and material redeposition. In order to achieve the asymmetry of the microstructures, the femtosecond laser is directed at an angle with respect to the sample surface. Two surfaces with microstructures angled at 45° and 10° with respect to the surface normal were fabricated. Droplet experiments were carried out with deionized water and a leveled hot plate to characterize the directional and self-propelling properties of the surfaces. It was found that the droplet motion direction is opposite of that for a surface with conventional ratchet microstructures reported in the literature. The new finding could not be explained by the widely accepted mechanism of asymmetric vapor flow. A new mechanism for a self-propelled droplet on asymmetric three-dimensional self-assembled microstructured surfaces is proposed.

Enhanced pool-boiling heat transfer and critical heat flux on femtosecond laser processed stainless steel surfaces.

In this paper, we present an experimental investigation of pool boiling heat transfer on multiscale (micro/nano) functionalized metallic surfaces. Heat transfer enhancement in metallic surfaces is very important for large scale high heat flux applications like in the nuclear power industry. The multiscale structures were fabricated via a femtosecond laser surface process (FLSP) technique, which forms self-organized mound-like microstructures covered by layers of nanoparticles. Using a pool boiling experimental setup with deionized water as the working fluid, both the heat transfer coefficients and critical heat flux were investigated. A polished reference sample was found to have a critical heat flux of 91 W/cm2 at 40 °C of superheat and a maximum heat transfer coefficient of 23,000 W/m2 K. The processed samples were found to have a maximum critical heat flux of 142 W/cm2 at 29 °C and a maximum heat transfer coefficient of 67,400 W/m2 K. It was found that the enhancement of the critical heat flux was directly related to the wetting and wicking ability of the surface which acts to replenish the evaporating liquid and delay critical heat flux. The heat transfer coefficients were also found to increase when the surface area ratio was increased as well as the microstructure peak-to-valley height. Enhanced nucleate boiling is the main heat transfer mechanism, and is attributed to an increase in surface area and nucleation site density.

A fundamental understanding of the dependence of the laser-induced breakdown spectroscopy (LIBS) signal strength on the complex focusing dynamics of femtosecond laser pulses on either side of the focus.

We correlate the focusing dynamics of 50 femtosecond (fs) laser radiation as it interacts with a silicon sample to laser-induced breakdown spectroscopy (LIBS) signal strength. Presented are concentric ring-shaped variations in the electric field in the prefocus region due to lens aberrations and nonsymmetry between the prefocus and post-focus beam profile as a result of continuum generation, occurring around the focus. Experimental results show different signal trends for both atmospheric and vacuum conditions, attributed to the existence of a continuum for the former. Lens aberrations effects on the LIBS signal strength are investigated using a plano-convex spherical lens and an aspherized achromatic lens. High-resolution scanning electron micrographs of the silicon surface after ablation, along with theoretical simulations, reveal the electric field patterns near the focus. The research results contribute to fundamental understanding of the basic physics of ultrashort, femtosecond laser radiation interacting with materials.

Extraordinary shifts of the Leidenfrost temperature from multiscale micro/nanostructured surfaces.

In the present work, the effects of surface chemistry and micro/nanostructuring on the Leidenfrost temperature are experimentally investigated. The functional surfaces were fabricated on a 304 stainless steel surface via femtosecond laser surface processing (FLSP). The droplet lifetime experimental method was employed to determine the Leidenfrost temperature for both machine-polished and textured surfaces. A precision dropper was used to control the droplet size to 4.2 µL and surface temperatures were measured by means of an embedded thermocouple. Extraordinary shifts in the Leidenfrost temperatures, as high as 175 °C relative to the polished surface, were observed with the laser-processed surfaces. These extraordinary shifts were attributed to nanoporosity, reduction in contact angle, intermittent liquid/solid contacts, and capillary wicking actions resulting from the presence of self-assembled nanoparticles formed on the surfaces. In addition to the shift in the Leidenfrost temperature, significant enhancement of the heat transfer in the film boiling regime was also observed for the laser-processed surfaces; water droplet evaporation times were reduced by up to 33% for a surface temperature of 500 °C.

Formation of multiscale surface structures on nickel via above surface growth and below surface growth mechanisms using femtosecond laser pulses.

The formation of self-organized micro- and nano-structured surfaces on nickel via both above surface growth (ASG) and below surface growth (BSG) mechanisms using femtosecond laser pulse illumination is reported. Detailed stepped growth experiments demonstrate that conical mound-shaped surface structure development is characterized by a balance of growth mechanisms including scattering from surface structures and geometric effects causing preferential ablation of the valleys, flow of the surface melt, and redeposition of ablated material; all of which are influenced by the laser fluence and the number of laser shots on the sample. BSG-mound formation is dominated by scattering, while ASG-mound formation is dominated by material flow and redeposition. This is the first demonstration to our knowledge of the use of femtosecond laser pulses to fabricate metallic surface structures that rise above the original surface. These results are useful in understanding the details of multi-pulse femtosecond laser interaction with metals.

Influence of WC-Co substrate pretreatment on diamond film deposition by laser-assisted combustion synthesis.

The quality of diamond films deposited on cemented tungsten carbide substrates (WC-Co) is limited by the presence of the cobalt binder. The cobalt in the WC-Co substrates enhances the formation of nondiamond carbon on the substrate surface, resulting in a poor film adhesion and a low diamond quality. In this study, we investigated pretreatments of WC-Co substrates in three different approaches, namely, chemical etching, laser etching, and laser etching followed by acid treatment. The laser produces a periodic surface pattern, thus increasing the roughness and releasing the stress at the interfaces between the substrate and the grown diamond film. Effects of these pretreatments have been analyzed in terms of microstructure and cobalt content. Raman spectroscopy was conducted to characterize both the diamond quality and compressive residual stress in the films.

Self assembled nanoparticle aggregates from line focused femtosecond laser ablation.

In this paper we present the use of a line focused femtosecond laser beam that is rastered across a 2024 T3 aluminum surface to produce nanoparticles that self assemble into 5-60 micron diameter domed and in some cases sphere-shaped aggregate structures. Each time the laser is rastered over initial aggregates their diameter increases as new layers of nanoparticles self assemble on the surface. The aggregates are thus composed of layers of particles forming discrete layered shells inside of them. When micron size aggregates are removed, using an ultrasonic bath, rings are revealed that have been permanently formed in the sample surface. These rings appear underneath, and extend beyond the physical boundary of the aggregates. The surface is blackened by the formation of these structures and exhibits high light absorption.