Tanmoy Maitra

On the Nanoengineering of Superhydrophobic and Impalement Resistant Surface Textures below the Freezing Temperature

The superhydrophobic behavior of nano- and microtextured surfaces leading to rebound of impacting droplets is of great relevance to nature and technology. It is not clear however, if and under what conditions this behavior is maintained when such surfaces are severely undercooled possibly leading to the formation of frost and icing. Here we elucidate key aspects of this phenomenon and show that the outcome of rebound or impalement on a textured surface is affected by air compression underneath the impacting drop and the time scale allowing this air to escape. Remarkably, drop impalement occurred at identical impact velocities, both at room and at very low temperatures (-30 °C) and featured a ringlike liquid meniscus penetration into the surface texture with an entrapped air bubble in the middle. At low temperatures, the drop contact time and receding dynamics of hierarchical surfaces were profoundly influenced by both an increase in the liquid viscosity due to cooling and a partial meniscus penetration into the texture. For hierarchical surfaces with the same solid fraction in their roughness, minimizing the gap between the asperities (both at micro- and nanoscales) yielded the largest resistance to millimetric drop impalement. The best performing surface impressively showed rebound at -30 °C for drop impact velocity of 2.6 m/s.

Spontaneous droplet trampolining on rigid superhydrophobic surfaces.

Spontaneous removal of condensed matter from surfaces is exploited in nature and in a broad range of technologies to achieve self-cleaning, anti-icing and condensation control. But despite much progress, our understanding of the phenomena leading to such behaviour remains incomplete, which makes it challenging to rationally design surfaces that benefit from its manifestation. Here we show that water droplets resting on superhydrophobic textured surfaces in a low-pressure environment can self-remove through sudden spontaneous levitation and subsequent trampoline-like bouncing behaviour, in which sequential collisions with the surface accelerate the droplets. These collisions have restitution coefficients (ratios of relative speeds after and before collision) greater than unity despite complete rigidity of the surface, and thus seemingly violate the second law of thermodynamics. However, these restitution coefficients result from an overpressure beneath the droplet produced by fast droplet vaporization while substrate adhesion and surface texture restrict vapour flow. We also show that the high vaporization rates experienced by the droplets and the associated cooling can result in freezing from a supercooled state that triggers a sudden increase in vaporization, which in turn boosts the levitation process. This effect can spontaneously remove surface icing by lifting away icy drops the moment they freeze. Although these observations are relevant only to systems in a low-pressure environment, they show how surface texturing can produce droplet–surface interactions that prohibit liquid and freezing water-droplet retention on surfaces.

Physics of icing and rational design of surfaces with extraordinary icephobicity.

Icing of surfaces is commonplace in nature and technology, affecting everyday life and sometimes causing catastrophic events. Understanding (and counteracting) surface icing brings with it significant scientific challenges that requires interdisciplinary knowledge from diverse scientific fields such as nucleation thermodynamics and heat transfer, fluid dynamics, surface chemistry, and surface nanoengineering. Here we discuss key aspects and findings related to the physics of ice formation on surfaces and show how such knowledge could be employed to rationally develop surfaces with extreme resistance to icing (extraordinary icephobicity). Although superhydrophobic surfaces with micro-, nano-, or (often biomimetic) hierarchical roughnesses have shown in laboratory settings (under certain conditions) excellent repellency and low adhesion to water down to temperatures near or below the freezing point, extreme icephobicity necessitates additional important functionalities. Other approaches, such as lubricant-impregnated surfaces, exhibit both advantages and serious limitations with respect to icing. In all, a clear path toward passive surfaces with extreme resistance to ice formation remains a challenge, but it is one well worth undertaking. Equally important to potential applications is scalable surface manufacturing and the ability of icephobic surfaces to perform reliably and sustainably outside the laboratory under adverse conditions. Surfaces should possess mechanical and chemical stability, and they should be thermally resilient. Such issues and related research directions are also addressed in this article.

Multifunctional Superhydrophobic Polymer/Carbon Nanocomposites: Graphene, Carbon Nanotubes, or Carbon Black?

Superhydrophobic surfaces resisting water penetration into their texture under dynamic impact conditions and offering simultaneously additional functionalities can find use in a multitude of applications. We present a facile, environmentally benign, and economical fabrication of highly electrically conductive, polymer-based superhydrophobic coatings, with impressive ability to resist dynamic water impalement through droplet impact. To impart electrical conductivity, the coatings were prepared by drop casting suspensions with loadings of different kinds of carbon nanoparticles, namely, carbon black (CB), carbon nanotubes (CNT), graphene nanoplatelets (GNP) and their combinations, in a fluoropolymer dispersion. At 50 wt % either CB or CNT, the nanocomposite coatings resisted impalement by water drops impacting at 3.7 m/s, the highest attainable speed in our setup. However, when tested with 5 vol % isopropyl alcohol-water mixture, i.e., a lower surface tension liquid posing a stiffer challenge with respect to impalement, only the CB coatings retained their impalement resistance behavior. GNP-based surfaces featured very high conductivity ∼1000 S/m, but the lowest resistance to water impalement. The optimal performance was obtained by combining the carbon fillers. Coatings containing CB:GNP:polymer = 1:1:2 showed both excellent impalement resistance (up to 3.5 m/s with 5 vol % IPA-water mixture drops) and electrical conductivity (∼1000 S/m). All coatings exhibited superhydrophobic and oleophilic behavior. To exemplify the additional benefit coming from this property, the CB and the optimal, combined CB/GNP coatings were used to separate mineral oil and water through filtration of their mixture.

Supercooled Water Drops Impacting Superhydrophobic Textures

Understanding the interaction of supercooled metastable water with superhydrophobic surface textures is of fundamental significance for unraveling the mechanisms of icing as well as of practical importance for the rational development of surface treatment strategies to prevent icing. We investigate the problem of supercooled water drops impacting superhydrophobic textures for drop supercooling down to -17 °C and find that increased viscous effects significantly influence all stages of impact dynamics, in particular, the impact and meniscus impalement behavior, with severe implications to water retention by the textures (sticky versus rebounding drop) and possible icing. Viscous effects in water supercooling conditions cause a reduction of drop maximum spreading (∼25% at an impact speed of 3 m/s for a millimetric drop) and can significantly decrease the drop recoil speed when the meniscus partially penetrates into the texture, leading to an increase of the contact time up to a factor of 2 in supercooling conditions compared to room temperature. We also show that meniscus penetration upon drop impact occurs with full penetration at the center, instead of ring shape, common to room temperature drop impact. To this end, we describe an unobserved mechanism for superhydrophobicity breakdown: unlike for room temperature drops, where transition from bouncing to sticky (impaled) behavior occurs sharply at the condition of full texture penetration, with a bubble captured at the point of impact, under supercooled conditions, the full penetration velocity threshold is increased markedly (increasing by ∼25%, from 2.8 to 3.5 m/s) and no bubble is entrapped. However, even though only partial texture penetration takes place, failure to completely dewet because of viscous effects can still prohibit complete supercooled drop rebound.

Unraveling wetting transition through surface textures with X-rays: Liquid meniscus penetration phenomena

In this report we show that synchrotron X-ray radiography is a powerful method to study liquid-air interface penetration through opaque microtextured surface roughness, leading to wetting transition. We investigate this wetting phenomenon in the context of sessile drop evaporation, and establish that liquid interface sinking into the surface texture is indeed dictated by the balance of capillary and Laplace pressures, where the intrinsically three-dimensional nature of the meniscus must be accounted for. Air bubble entrapment in the texture underneath impacting water drops is also visualized and the mechanisms of post-impact drop evaporation are discussed.

On the shedding of impaled droplets: The role of transient intervening layers.

Maintaining the non-wetting property of textured hydrophobic surfaces is directly related to the preservation of an intervening fluid layer (gaseous or immiscible liquid) between the droplet and substrate; once displaced, it cannot be recovered spontaneously as the fully penetrated Wenzel wetting state is energetically favorable. Here, we identify pathways for the “lifting” of droplets from the surface texture, enabling a complete Wenzel-to-Cassie-Baxter wetting state transition. This is accomplished by the hemiwicking of a transient (limited lifetime due to evaporation) low surface tension (LST) liquid, which is capable of self-assembling as an intervening underlayer, lifting the droplet from its impaled state and facilitating a skating-like behavior. In the skating phase, a critical substrate tilting angle is identified, up to which underlayer and droplet remain coupled exhibiting a pseudo-Cassie-Baxter state. For greater titling angles, the droplet, driven by inertia, detaches itself from the liquid intervening layer and transitions to a traditional Cassie-Baxter wetting state, thereby accelerating and leaving the underlayer behind. A model is also presented that elucidates the mechanism of mobility recovery. Ultimately, this work provides a better understanding of multiphase mass transfer of immiscible LST liquid-water mixtures with respect to establishing facile methods towards retaining intervening layers.

Detergency and Its Implications for Oil Emulsion Sieving and Separation

Separating petroleum hydrocarbons from water is an important problem to address in order to mitigate the disastrous effects of hydrocarbons on aquatic ecosystems. A rational approach to address the problem of marine oil-water separation is to disperse the oil with the aid of surfactants in order to minimize the formation of large slicks at the water surface and to maximize the oil-water interfacial area. Here we investigate the fundamental wetting and transport behavior of such surfactant-stabilized droplets and the flow conditions necessary to perform sieving and separation of these stabilized emulsions. We show that, for water-soluble surfactants, such droplets are completely repelled by a range of materials (intrinsically underwater superoleophobic) due to the detergency effect; therefore, there is no need for surface micro-/nanotexturing or chemical treatment to repel the oil and prevent fouling of the filter. We then simulate and experimentally investigate the effect of emulsion flow rate on the transport and impact behavior of such droplets on rigid meshes to identify the minimum pore opening (w) necessary to filter a droplet with a given diameter (d) in order to minimize the pressure drop across the mesh-and therefore maximize the filtering efficiency, which is strongly dependent on w. We define a range of flow conditions and droplet sizes where minimum droplet deformation is to be expected and therefore find that the condition of w ≈ d is sufficient for efficient separation. With this new understanding, we demonstrate the use of a commercially available filter-without any additional surface engineering or functionalization-to separate oil droplets (d < 100 μm) from a surfactant-stabilized emulsion with a flux of ∼11,000 L m-2 h-1 bar-1. We believe these findings can inform the design of future oil separation materials.

Thermal Transport in Micro- and Nanoscale Systems

Small scale (micro/nanoscale) heat transfer has broad and exciting range of applications. Heat transfer at small scale quite naturally is influenced sometimes dramatically with high surface area to volume ratios. This in effect means that heat transfer in small scale devices and systems is influenced by surface treatment and surface morphology. Importantly, interfacial dynamic effects are at least non-negligible and there is a strong potential to engineer the performance of such devices using the progress in micro and nanomanufacturing technologies. With this motivation, the emphasis here is on heat conduction and convection. The chapter starts with a broad introduction to Boltzmann Transport equation which can capture the physics of small scale heat transport and outlining the reasons why small scale transport distinct from classical micro scale heat transport. Among applications, examples are thermoelectric and thermal interface materials where micro and nanofabrication has led to impressive figure of merits and thermal management performance. Basic of phonon transport and its manipulation through nanostructuring materials are discussed in detail. Small scale single phase convection and the crucial role it has played in developing the thermal management solutions for next generation of electronics and energy harvesting devices are discussed as next topic. Features of micro cooling platforms and physics of optimized thermal transport using micro channel manifold heat sinks are discussed in detail along with a discussion of how such systems also facilitate use of low grade, waste heat from data centres and photovoltaic modules. Phase changes process and their control using surface micro/nanostructure are discussed next. Among the feature considered, the first are microscale heat pipes where capillary effects play an important role. Next the role of nanostructures in controlling nucleation and mobility in boiling, condensation and icing are discussed great detail. Special emphasis is placed on the limitations of current surface and device manufacture technologies while also