Modeling Superhydrophobic Contact Angles and Wetting Transition

It is well known that surface roughness has a very important effect on superhydrophobicity.The Wenzel and Cassie-Baxter models,which correspond to the homogeneous and heterogeneous wetting respectively,are currently primary instructions for designing superhydrophobic surfaces.However,the particular drop shape that a drop exhibits might depend on how it is formed. A water drop can occupy multiple equilibrium states,which relate to different local minimal energy.In some cases,both equilibrium states can even co-exist on a same substrate.Thus the apparent contact angles may vary and have different values.We discuss how the Wenzel and Cassie-Baxter equations determine the homogeneous and heterogeneous wetting theoretically. Contact angle analysis on hierarchical surface structure and contact angle hysteresis has been put specific attention.In particular, we study the energy barrier of transition from Cassie-Baxter state to Wenzel state,based on existing achievement by previous researchers,to determine the possibility of the transition and how it can be interpreted.It has been demonstrated that surface roughness and geometry will influence the energy required for a drop to get into equilibrium,no matter it is homogeneous or heterogeneous wetting.

Thermal rectification induced by Wenzel–Cassie wetting state transition on nano-structured solid–liquid interfaces

Thermal rectification refers to the phenomenon by which the magnitude of the heat flux in one direction is much larger than that in the opposite direction.In this study,we propose to implement the thermal rectification phenomenon in an asymmetric solid–liquid–solid sandwiched system with a nano-structured interface.By using the non-equilibrium molecular dynamics simulations,the thermal transport through the solid–liquid–solid system is examined,and the thermal rectification phenomenon can be observed.It is revealed that the thermal rectification effect can be attributed to the significant difference in the interfacial thermal resistance between Cassie and Wenzel states when reversing the temperature bias.In addition,effects of the liquid density,solid–liquid bonding strength and nanostructure size on the thermal rectification are examined.The findings may provide a new way for designs of certain thermal devices.

Numerical Study of Wetting Transitions on Biomimetic Surfaces Using a Lattice Boltzmann Approach with Large Density Ratio

The hydrophobicity of natural surfaces has drawn much attention of scientific communities in recent years. By mimicking natural surfaces, the manufactured biomimetic hydrophobic surfaces have been widely applied to green technologies such as self-cleaning surfaces. Although the theories for wetting and hydrophobicity have been developed, the mechanism of wetting transitions between heterogeneous wetting state and homogeneous wetting state is still not fully clarified. As understanding of wetting transitions is crucial for manufacturing a biomimetic superhydrophobic surface, more fundamental discussions in this area should be carried out. In the present work, the wetting transitions are numerically studied using a phase field lattice Boltzmann approach with large density ratio, which should be helpful in understanding the mechanism of wetting transitions. The dynamic wetting transition processes between Cassie-Baxter state and Wenzel state are presented, and the energy barrier and the gravity effect on transition are discussed. It is found that the two wetting transition processes are irreversible for specific inherent contact angles and have different transition routes, the energy barrier exists on an ideally patterned surface and the gravity can be crucial to overcome the energy barrier and trigger the transition.

Wetting transition energy curves for a droplet on a square-post patterned surface

Due to the property of water repellence, biomimetic superhydrophobic surfaces have been widely applied to green technologies, in turn inducing wider and deeper investigations on superhydrophobic surfaces. Theoretical, experimental and numerical studies on wetting transitions have been carried out by researchers, but the mechanism of wetting transitions between Cassie-Baxter state and Wenzel state, which is crucial to develop a stable superhydrophobic surface, is still not fully understood. In this paper, the flee energy curves based on the transition processes are presented and discussed in detail. The exis- tence of energy barriers with or without consideration of the gravity effect, and the irreversibility of wet- ting transition are discussed based on the presented energy curves. The energy curves show that different routes of the Cassie-to-Wenzel transition and the reverse transition are the main reason for the irre- versibility. Numerical simulations are implemented via a phase field lattice Boltzmann method of large density ratio, and the simulation results show good consistency with the theoretical analysis.

Gradient Wetting Transition from the Wenzel to Robust Cassie-Baxter States along Nanopillared Cicada Wing and Underlying Mechanism

Gradient wettability is important for some living organisms.Herein,the dynamic responses of water droplets impacting on the surfaces of four regions along the wing vein of cicada Cryptotympana atratafabricius are investigated.It is revealed that a gradient wetting behavior from hydrophilicity(the Wenzel state)to hydrophobicity and further to superhydrophobicity(the Cassie-Baxter state)appears from the foot to apex of the wing.Water droplets impacting on the hydrophilic region of the wing cannot rebound,whereas those impacting on the hydrophobic region can retract and completely rebound.The hydrophobic region exhibits robust water-repelling performance during the dynamic droplet impact.Moreover,a droplet sitting on the hydrophobic region can recover its spherical shape after squeezed to a water film as thin as 0.45 mm,and lossless droplet transportation can be achieved at the region.Based on the geometric parameters of the nanopillars at the hydrophilic and hydrophobic regions on the cicada wing,two wetting models are developed for elucidating the mechanism for the gradient wetting behavior.This work directs the design and fabrication of surfaces with gradient wetting behavior by mimicking the nanopillars on cicada wing surface.

Fabrication of pillar-array superhydrophobic silicon surface and thermodynamic analysis on the wetting state transition

Textured silicon （Si） substrates decorated with regular microscale square pillar arrays of nearly the same side length, height, but different intervals are fabricated by inductively coupled plasma, and then silanized by self-assembly octadecyl- trichlorosilane （OTS） film. The systematic water contact angle （CA） measurements and micro/nanoscale hierarchical rough structure models are used to analyze the wetting behaviors of original and silanized textured Si substrates each as a function of pillar interval-to-width ratio. On the original textured Si substrate with hydrophilic pillars, the water droplet possesses a larger apparent CAs （〉 90~） and contact angle hysteresis （CAH）, induced by the hierarchical roughness of microscale pil- lar arrays and nanoscale pit-like roughness. However, the silanized textured substrate shows superhydrophobicity induced by the low free energy OTS overcoat and the hierarchical roughness of microscale pillar arrays, and nanoscale island-like roughness. The largest apparent CA on the superhydrophobic surface is 169.8~. In addition, the wetting transition of a gently deposited water droplet is observed on the original textured substrate with pillar interval-to-width ratio increasing. Furthermore, the wetting state transition is analyzed by thermodynamic approach with the consideration of the CAH effect. The results indicate that the wetting state changed from a Cassie state to a pseudo-Wenzel during the transition.

Wetting Behaviours of a Single Droplet on Biomimetic Micro Structured Surfaces

Natural surfaces with super hydrophobic properties often have micro or hierarchical structures.In this paper, the wettingbehaviours of a single droplet on biomimetic micro structured surfaces with different roughness parameters are investigated.Atheoretical model is proposed to study wetting transitions.The results of theoretical analysis are compared with those of experimentindicating that the proposed model can effectively predict the wetting transition.Furthermore, a numerical simulationbased on the meso scale Lattice Boltzmann Method （LBM） is performed to study dynamic contact angles, contact lines, andlocal velocity fields for the case that a droplet displays on the micro structured surface.A spherical water droplet with r= 15 μmfalls down to a biomimetic square-post patterned surface under the force of gravity with an initial velocity of 0.01 m·sand aninitial vertical distance of 20 μm from droplet centre to the top of pots.In spite of a higher initial velocity, the droplet can stillstay in a Cassie state; moreover, it reaches an equilibrium state at t≈17.5 ms, when contact angle is 153.16° which is slightlylower than the prediction of Cassie-Baxter’s equation which gives θ=154.40°.

Residual stress induced wetting variation on electric brush-plated Cu film

Nanocrystalline Cu film with a mirror surface finishing is prepared by the electric brush-plating technique. The as- prepared Cu film exhibits a superhydrophilic behavior with an apparent water contact angle smaller than 10°. A subsequent increase in the water contact angle and a final wetting transition from inherent hydrophilicity with water contact angle smaller than 90° to apparent hydrophobicity with water contact angle larger than 90° are observed when the Cu film is subjected to natural aging. Analysis based on the measurement of hardness with nanoindentation and the theory of the bond-order-length-strength correlation reveals that this wetting variation on the Cu film is attributed to the relaxation of residual stress generated during brush-plating deposition and a surface hydrophobization role associated with the broken bond polarization induced by surface nanostructure.

Effect of Substrate-Water Interaction on the Wetting Behavior in Water-Oil and Substrate-Water-Oil Systems

The effects of the substrate-water interaction on the wetting behavior in water-oil and surfactant-water-oil systems confined by one substrate which has the preferential interaction to one species of particles have been investigated by using the free energy analysis and discontinuous molecular dynamic simulations. As the preferential interaction between the substrate and water particles varies from small repulsion to large attraction, the partial drying, partial wetting and complete wetting state are observed in sequence. In addition, the wetting behavior of surfactant aqueous solution on the substrate is not only dependent on the interaction, but also limited by the maximum equilibrium concentration of surfactants at the interface.

Transition of super-hydrophobic states of droplet on rough surface

Twelve samples with periodic array square pillars microstructure were prepared on the silicon wafer by plasma etching techniques, on which space b of the square pillars increased from 5 to 60 μm. In order to study the effect ofb on the wettability of the rough surface, the effects of apparent contact angle （CA） and sliding angle （a） of the droplet on the rough surface were measured with the contact angle meter. The results show that the experimental values of CA well agree with the classical wetting theory and a decreases with the increase of b. Two drop shapes exist on the samples＇ surface, corresponding to the Cassie state and the Wenzel state respectively. The contact state in which a drop would settle depends typically on the size of b. On the role of gravitation, the irreversible transition of a drop from Cassie state to Wenzel state should occur at a certain space of the square pillars. Since the transition has implications on the application of super-hydrophobic rough surfaces, theoretically, the prediction of wetting state transition on square pillar array micro-structured surfaces provides an intuitionistic guidance for the design of steady superhydrophobic surfaces.

Role of Multi-scale Hierarchical Structures in Regulating Wetting State and Wetting Properties of Structured Surfaces

Amplifying the intrinsic wettability of substrate material by changing the solid/liquid contact area is considered to be the main mechanism for controlling the wettability of rough or structured surfaces.Through theoretical analysis and experimental exploration,we have found that in addition to this wettability structure amplification effect,the surface structure also simultaneously controls surface wettability by regulating the wetting state via changing the threshold Young angles of the Cassie-Baxter and Wenzel wetting regions.This wetting state regulation effect provides us with an alternative strategy to overcome the inherent limitation in surface chemistry by tailoring surface structure.The wetting state regulation effect created by multi-scale hierarchical structures is quite significant and plays is a crucial role in promoting the superhydrophobicity,superhydrophilicity and the transition between these two extreme wetting properties,as well as stabilizing the Cassie-Baxter superhydrophobic state on the fabricated lotus-like hierarchically structured Cu surface and the natural lotus leaf.

Discussion of the“warming and wetting”trend and its future variation in the drylands of Northwest China under global warming

Since Shi et al.proposed that the climate in the drylands of Northwest China experienced a significant transition from a“warming and drying”trend to a“warming and wetting”trend in the 1980s,researchers have conducted numerous studies on the variations in precipitation and humidity in the region and even in arid Central Asia.In particular,the process of the“warming and wetting”trend by using obtained measurement data received much attention.However,there remain uncertainties about whether the“warming and wetting”trend has paused and what its future variations may be.In this study,we examined the spatiotemporal variations in temperature,precipitation,the aridity index(AI),vegetation,and runoff during 1950-2019.The results showed that the climate in the drylands of Northwest China and the northern Tibetan Plateau is persistently warming and wetting since the 1980s,with an acceleration since the 1990s.The precipitation/humidity variations in North China,which are mainly influenced by summer monsoon,are generally opposite to those in the drylands of Northwest China.This reverse change is mainly controlled by an anomalous anticyclone over Mongolia,which leads to an anomalous easterly wind,reduced water vapor output,and increased precipitation in the drylands of Northwest China.While it also causes an anomalous descending motion,increased water vapor divergence,and decreased precipitation in North China.Precipitation is the primary controlling factor of humidity,which ultimately forms the spatiotemporal pattern of the“westerlies-dominated climatic regime”of antiphase precipitation/humidity variations between the drylands of Northwest China and monsoonal region of North China.The primary reasons behind the debate of the“warming and wetting”trend in Northwest China were due to the use of different time series lengths,regional ranges,and humidity indices in previous analyses.Since the EC-Earth3 has a good performance for simulating precipitation and humidity in Northwest and North China.By using its simulated results,we found a wetting trend in the drylands of Northwest China under low emission scenarios,but the climate will gradually transition to a“warming and drying”trend as emissions increase.This study suggests that moderate warming can be beneficial for improving the ecological environment in the drylands of Northwest China,while precipitation and humidity in monsoon-dominated North China will persistently increase under scenarios of increased emissions.

Interdecadal Variability of East Asian Summer Monsoon Precipitation over 220 Years (1777-1997)

In this study, long-term （1777–1997） precipitation data for Seoul, Korea, wetness indices from eastern China, and modern observations are used to identify the interdecadal variability in East Asian summer monsoon precipitation over the last 220 years. In the East Asian monsoon region, two long-term timescales of dry–wet transitions for the interdecadal variability and quasi-40-and quasi-60-year timescales are dominant in the 220-year precipitation data of Seoul, as well as in the wetness indices over China. The wet and dry spells between Seoul （southern China） and northern China are out-of-phase （out-of-phase） at the quasi-60-year timescale, and in-phase （out-of-phase by approximately 90 ？ before 1900 and in-phase after 1900） at the quasi-40-year timescale. In particular, during the last century, the dominant long-term timescales over East Asia tend to decrease from the quasi-60-year to the quasi-40-year with increasing time. The dominant quasi-40-year and quasi-60-year timescales of the Seoul precipitation in Korea are strongly correlated with these timescales of the northern Pacific Ocean.

Intersubband, interband transitions, and optical properties of two vertically coupled hemispherical quantum dots with wetting layers

The electron and heavy hole energy levels of two vertically coupled In As hemispherical quantum dots/wetting layers embedded in a Ga As barrier are calculated numerically. As the radius increases, the electronic energies increase for the small base radii and decrease for the larger ones. The energies decrease as the dot height increases. The intersubband and interband transitions of the system are also studied. For both, a spectral peak position shift to lower energies is seen due to the vertical coupling of dots. The interband transition energy decreases as the dot size increases, decreases for the dot shapes with larger heights, and reaches a minimum for coupled semisphere dots.

A Study of the Truncated Square Pyramid Geometry for Enhancement of Super-hydrophobicity

Super-hydrophobic surfaces are quite common in nature,inspiring people to continually explore its water-repellence property and applications to our lives.It has been generally agreed that the property of super-hydrophobicity is mainly contributed by the microscale or nanoscale(or even smaller)architecture on the surface.Besides,there is an energy barrier between the Cassie-Baxter wetting state and the Wenzel wetting state.An optimized square post micro structure with truncated square pyramid geometry is introduced in this work to increase the energy barrier,enhancing the robustness of super-hydrophobicity.Theoretical analysis is conducted based on the wetting transition energy curves.Numerical simulation based on a phase-field lattice Boltzmann method is carried out to verify the theoretical analysis.The numerical simulation agrees well with the theoretical analysis,showing the positive significance of the proposed micro structure.Furthermore,another novel micro structure of rough surface is presented,which combines the advantages of truncated pyramid geometry and noncommunicating roughness elements.Theoretical analysis shows that the novel micro structure of rough surface can effectively hinder the Cassie-Baxter state to Wenzel state transition,furthefly enhancing the robustness of the surface hydrophobicity.

Experiment on gas-liquid displacement in a capillary

It has been reported in recent experimental and numerical studies that the forced gas-liquid displacement in a partially wettable capillary tube can give rise to entrainment of a liquid film and generation of Taylor bubbles at a large displacement rate.However,simulations and hydrodynamic theory of Gao et al.(J.Fluid Meeh.,2019,vol 859:308-320)predicted an abrupt drop of the contact line velocity Ca_(cl)at the onset of wetting transition,which conflicted with the experiments of Zhao et al.(Phys.Rev.Lett.,2018,vol 120:084501),who suggested a continuous variation of Ca_(cl).To resolve this discrepancy,we performed experiments of gas-liquid displacement,focusing on the contact line velocity close to the threshold.It is found that Ca_(cl) is indeed discontinuous,confirming the validity of the hydrodynamic description of the moving contact line.After an abrupt drop,Ca_(cl)increases to a constant for a slight raise of the displacement rate.The failure of detecting this discontinuity in previous experiments is due to the low resolution of the displacement rate.The propagating velocity and the length of the generated bubbles are presented and agree well with the existing theory.Variation of the liquid slug length with the displacement rate is also presented.