Empirical study and prediction of liquids retention on structured polymer surfaces

Liquids' contact angle hysteresis and critical retention volumes on five commonly used plastics with surface structures were studied. The chevron‐like groove structures, which are orthogonally arranged, make the liquid–solid contact line elongated while the droplet found staying in the Wenzel state. Various dimensions of surface structures were represented by contact length ratio σ. Advancing and receding contact angles of liquids on polymer surfaces with various conditions were reported. Reduced hysteresis H, which links between advancing and receding contact angles, was also studied and found to extend its availability on structured surfaces. The research found that surface structures have linear effects on liquids' advancing contact angles in the range of σ = 1.0 to 1.42. Linear regression analysis was hence proposed to predict advancing contact angles, and the results indicate that approximate 80% of data points have less than 6% error. An empirical model, which adopts liquid–solid surface tension as the source of liquids' retention force, was proposed to estimate liquids' critical retention volumes on inclined surfaces. The proposed model found good agreements with existing experiment data and demonstrated its superiority over previous ones. The present model provides an approach to predict liquids' storage/repellency on structured surfaces when the advancing contact angles are predictable. Copyright © 2016 John Wiley & Sons, Ltd.     

Study of the advancing and receding contact angles: liquid sorption as a cause of contact angle hysteresis

Two types of experiments were used to study the behavior of both advancing and receding contact angles, namely the dynamic one-cycle contact angle (DOCA) and the dynamic cycling contact angle (DCCA) experiments. For the preliminary study, DOCA measurements of different liquids on different solids were performed using an automated axisymmetric drop shape analysis-profile (ADSA-P). From these experimental results, four patterns of receding contact angle were observed: (1) time-dependent receding contact angle; (2) constant receding contact angle; (3) 'stick/slip'; (4) no receding contact angle. For the purpose of illustration, results from four different solid surfaces are shown. These solids are: FC-732-coated surface; poly(methyl methacrylate/n-butyl methacrylate) [P(MMA/nBMA)]; poly(lactic acid) (DL-PLA); and poly(lactic/glycolic acid) 50/50 (DL-PLGA 50/50). Since most of the surfaces in our studies exhibit time dependence in the receding contact angle, a more extended study was conducted using only FC-732-coated surfaces to better understand the possible causes of decreasing receding contact angle and contact angle hysteresis. Contact angle measurements of 21 liquids from two homologous series (i.e. n-alkanes and 1-alcohols) and octamethylcyclotetrasiloxane (OCMTS) on FC-732-coated surfaces were performed. It is apparent that the contact angle hysteresis decreases with the chain length of the liquid. It was found that the receding contact angle equals the advancing angle when the alkane molecules are infinitely large. These results strongly suggest that the chain length and size of the liquid molecule could contribute to contact angle hysteresis phenomena. Furthermore, DCCA measurements of six liquids from the two homologous series on FC-732-coated surfaces were performed. With these experimental results, one can construe that the time dependence of contact angle hysteresis on relatively smooth and homogeneous surfaces is mainly caused by liquid retention/sorption. The results also suggested that the contact angle hysteresis will eventually approach a steady state, where the rate of liquid retention-evaporation or sorption process would balance out each other. If the existence of contact angle hysteresis can be attributed to liquid sorption/retention, one should only use the advancing contact angles (measured on a dry surface) in conjunction with Young's equation for surface energetic calculations.     

Self-organised microdots formed by dewetting in a highly volatile liquid

Dewetting induced self-organisation was used to prepare an ordered microstructure from a highly volatile liquid. Dewetting of an evaporating iron oxide precursor solute on silicon substrate resulted in arrays of microdots with nearly hexagonal and tetragonal symmetries. Ordered structures form either by stick-slip motion or fingering instability at the receding contact line of evaporating droplets. Subsequent thermal treatment at 550 °C yields crystalline Fe(2)O(3) microdots with a diameter range of 1-4 μm. The size, density and shape of the microdots can be changed by using patterned substrates with different surface energies.     

Anomalous contact angle hysteresis of a captive bubble: advancing contact line pinning

Contact angle hysteresis of a sessile drop on a substrate consists of continuous invasion of liquid phase with the advancing angle (θ(a)) and contact line pinning of liquid phase retreat until the receding angle (θ(r)) is reached. Receding pinning is generally attributed to localized defects that are more wettable than the rest of the surface. However, the defect model cannot explain advancing pinning of liquid phase invasion driven by a deflating bubble and continuous retreat of liquid phase driven by the inflating bubble. A simple thermodynamic model based on adhesion hysteresis is proposed to explain anomalous contact angle hysteresis of a captive bubble quantitatively. The adhesion model involves two solid–liquid interfacial tensions (γ(sl) > γ(sl)′). Young’s equation with γ(sl) gives the advancing angle θ(a) while that with γ(sl)′ due to surface rearrangement yields the receding angle θ(r). Our analytical analysis indicates that contact line pinning represents frustration in surface free energy, and the equilibrium shape corresponds to a nondifferential minimum instead of a local minimum. On the basis of our thermodynamic model, Surface Evolver simulations are performed to reproduce both advancing and receding behavior associated with a captive bubble on the acrylic glass.     

Contact angle relaxation on low energy surfaces

The spontaneous relaxation of the water—vapour interface, in contact with the “low energy” solids poly(ethylene terephthalate) (PET) and poly(methyl methacrylate) (PMMA), has been investigated after forced advancing and receding movement. A tensiometric apparatus has been used to probe the three-phase contact zone during relaxation for periods of up to 24 h. The measured force—time trace differs from that which might be anticipated, due to extraneous phenomena such as bulk evaporation/condensation/absorption. It is clear that even for a pure low viscosity liquid such as water, an imbalance in interfacial energies in the neighbourhood of the three-phase contact line (TPCL) exists for extended periods. Measurements have been made at both high and low water vapour pressures. In the advancing case, the TPCL is pinned and equilibration occurs via an essentially evaporative mechanism. In the receding case, the TPCL is mobile and the approach to equilibrium, which also occurs by an evaporative mechanism, is much slower. Indeed our results lead us to question whether equilibrium in the receding case is experimentally accessible. Contact angle hysteresis was found to be significantly smaller in magnitude than that typically measured within seconds or a few minutes of the cessation of forced TPCL movement.     

Modeling contact angle hysteresis of a liquid droplet sitting on a cosine wave-like pattern surface

A liquid droplet sitting on a hydrophobic surface with a cosine wave-like square-array pattern in the Wenzel state is simulated by using the Surface Evolver to determine the contact angle. For a fixed drop volume, multiple metastable states are obtained at two different surface roughnesses. Unusual and non-circular shape of the three-phase contact line of a liquid droplet sitting on the model surface is observed due to corrugation and distortion of the contact line by structure of the roughness. The contact angle varies along the contact line for each metastable state. The maximum and minimum contact angles among the multiple metastable states at a fixed viewing angle correspond to the advancing and the receding contact angles, respectively. It is interesting to observe that the advancing/receding contact angles (and contact angle hysteresis) are a function of viewing angle. In addition, the receding (or advancing) contact angles at different viewing angles are determined at different metastable states. The contact angle of minimum energy among the multiple metastable states is defined as the most stable (equilibrium) contact angle. The Wenzel model is not able to describe the contact angle along the three-phase contact line. The contact angle hysteresis at different drop volumes is determined. The number of the metastable states increases with increasing drop volume. Drop volume effect on the contact angles is also discussed.     

Line energy and the relation between advancing, receding, and young contact angles

The line energy associated with the triple phase contact line is a function of local surface defects (chemical and topographical); however, it can still be calculated from the advancing and receding contact angles to which those defects give rise. In this study an expression for the line energy associated with the triple phase contact line is developed. The expression relates the line energy to the drop volume, the interfacial energies, and the actual contact angle (be it advancing, receding, or in between). From the expression we can back calculate the equilibrium Young contact angle, theta0, as a function of the maximal advancing, thetaA, and minimal receding, thetaR, contact angles. To keep a certain maximal hysteresis between advancing and receding angles, different line energies are required depending on the three interfacial energies and the drop's volume V. We learn from the obtained expressions that the hysteresis is determined by some dimensionless parameter, K, which is some normalized line energy. The value of K required to keep a constant hysteresis (thetaA-thetaR) rises to infinity as we get closer to theta0 = 90 degrees.     

Unsteady motion of receding contact lines of surfactant solutions: the role of surfactant re-self-assembly

Re-self-assembly of surfactant molecules must occur at moving contact lines of soluble surfactant solutions. Molecules are transported into and out of the contact line region from four sources: the three interfaces meeting at the contact line and the fluid confined between the solid-liquid and liquid-vapor interfaces. As molecules move among these sources at the contact line, they must rearrange. The dynamics of this re-self-assembly has been shown to have a dominating effect on the structure of advancing contact lines, causing unsteady motion and complex structure of the contact line. It might be assumed that the re-self-assembly for receding contact lines leads to more steady contact line movement. However, in this article we show that for a wide variety of systems this is not true. Quasi-static distortions of the contact line occur as it retreats because of the inability of the surfactant to completely re-self-assemble at localized positions along the contact line.     

Guided alignment and positioning of single DNA molecules by a structured contact line on a block copolymer surface

A nanostructured dynamical contact line is generated when the meniscus of a droplet of water solution is moving on the structured surface of a thin film of a block copolymer of poly(styrene-b-methyl methacrylate) (PS-b-PMMA) because of the difference in the water contact angles on PS and PMMA. Such a structured receding contact line extends DNA molecules as in the molecular combing process. More importantly, it aligns DNA molecules following the position and orientation of the PMMA domains on the surface. The driving force of this phenomenon is discussed as the lateral motion of the locally modified contact line.     

Application of photosensitive polyimides as alignment layer to optical switching devices of a nematic liquid crystal

We have explored the change in alignment of a nematic liquid crystal, 4'-pentyl-4-cyanobiphenyl (5CB) with three types of photosensitive polyimide as the alignment layer by photoirradiation at 366 nm. The photosensitive polyimide alignment layer induced a reversible change in alignment of 5CB. It was observed that the 5CB molecules became aligned from homogeneous alignment to homeotropic on photoirradiation with a d.c. electric field as a bias, and reversed to the homogeneous state when photoirradiation was ceased. This result indicates that optical switching could be repeated by on and off switching of the excitation light at 366 nm. The optical switching of the nematic liquid crystal might be mainly due to a photophysical change in the polyimide surface which is affected by the chemical structures of the polyimides at the temperature at which 5CB exhibits a nematic phase. The optical switching of nematic liquid crystals with photosensitive polyimides as the alignment layer is a novel driving method for nematic liquid crystals.     

Line tension effects for liquid droplets on circular surface domains

We study the morphologies of single liquid droplets wetting a substrate in the presence of the line tension of the three-phase contact line. On a homogeneous substrate, the line tension leads to a discontinuous unbinding of the droplet if its volume is decreased below a critical value. For a droplet wetting a structured surface with a circular domain, a line tension contrast gives rise to discontinuous depinning transitions of the contact line from the domain boundary as the droplet volume is varied. We calculate the corresponding free energy bifurcation diagram analytically for axisymmetric droplet shapes. Numerical minimization of the droplet free energy shows that line tension contrasts can stabilize nonaxisymmetric droplet shapes, thus modifying the bifurcation diagram. These latter shapes should be accessible to experiments and can be used to reveal the presence of a line tension contrast.     

Estimation of surface free energies and hamaker constants for fibrous solids by wetting force measurements

Wetting force at three-phase line was measured by the Wilhelmy technique using fibrous solids/liquid/liquid systems. Advancing and receding contact angles were calculated from the wetting forces during fiber immersion and emersion. The obtained results showed that contact angle hysteresis was due to the heterogeneity of the fiber surfaces. The dispersive and polar components of surface free energies of the fibers were determined from the advancing and receding contact angles, respectively. The Hamaker constants of the fibers were estimated from the dispersive components of their surface free energies.     

Evaporative characteristics of sessile nanofluid droplet on micro‐structured heated surface

Micro‐structure patterned substrates attract our attention due to the special and programmable wettabilities. The interaction between the liquid and micro/nano structures gives rise to controllable spreading and thus evaporation. For exploration of the application versatility, the introduction of nanoparticles in liquid droplet results in interaction among particles, liquid and microstructures. In addition, temperature of the substrates strongly affects the spreading of the contact line and the evaporative property. The evaporation of sessile droplets of nanofluids on a micro‐grooved solid surface is investigated in terms of liquid and surface properties. The patterned nickel surface used in the experiments is designed and fabricated with circular and rectangular shaped pillars whose size ratios between interval and pillars is fixed at 5. The behavior is firstly compared between nanofluid and pure liquid on substrates at room temperature. For pure water droplet, the drying time is relatively longer due to the receding of contact line which slows down the liquid evaporation. Higher concentrations of nanoparticles tend to increase the total evaporation time. With varying concentrations of graphite at nano scale from 0.02% to 0.18% with an interval at 0.04% in water droplets and the heating temperature from 22 to 85°C, the wetting and evaporation of the sessile droplets are systematically studied with discussion on the impact parameters and the resulted liquid dynamics as well as the stain. The interaction among the phases together with the heating strongly affects the internal circulation inside the droplet, the evaporative rate and the pattern of particles deposition.     

Application of photosensitive polyimides as alignment layer to optical switching devices of a nematic liquid crystal

We have explored the change in alignment of a nematic liquid crystal, 4'-pentyl-4-cyanobiphenyl (5CB) with three types of photosensitive polyimide as the alignment layer by photoirradiation at 366 nm. The photosensitive polyimide alignment layer induced a reversible change in alignment of 5CB. It was observed that the 5CB molecules became aligned from homogeneous alignment to homeotropic on photoirradiation with a d.c. electric field as a bias, and reversed to the homogeneous state when photoirradiation was ceased. This result indicates that optical switching could be repeated by on and off switching of the excitation light at 366 nm. The optical switching of the nematic liquid crystal might be mainly due to a photophysical change in the polyimide surface which is affected by the chemical structures of the polyimides at the temperature at which 5CB exhibits a nematic phase. The optical switching of nematic liquid crystals with photosensitive polyimides as the alignment layer is a novel driving method for nematic liquid crystals.     

A refractive tilting-plate technique for measurement of dynamic contact angles

The contact angle is a critical parameter in liquid interface dynamics ranging from liquid spreading on a solid surface on earth to liquid motion in partially filled containers in space. A refractive tilting-plate technique employing a scanning laser beam is developed to conduct an experimental study of a moving contact line, with the intention of making accurate measurements of the contact angle. The technique shows promise as an accurate and potentially fully automated means to determine the velocity dependence of the contact angle at the intersection of the interface between two transparent fluids with a transparent solid surface. Ray tracing calculations are included to reinforce the measurement concept. The principal experiments were conducted at speeds ranging from 0.05 to 1.00 mm/s, both advancing and receding, using an immiscible liquid pair (nonane/formamide) in contact with glass. The contact angle was found to depend for practical purposes only on the sign of the velocity and not on its magnitude for the range of velocities studied. Other observations revealed a bimodal behavior of the contact line that depends on which liquid first contacts the glass, with resulting drift in the dynamic contact angle with time.     

Advancing and receding wetting behavior of a droplet on a narrow rectangular plane

The contact angle (CA) measurements are generally performed on a large planar surface of a specific substrate with the width larger than the droplet size. In this study, the contact angle hysteresis on a narrow rectangular plane with a width smaller than the droplet size is experimentally studied through the inflation–deflation process by the needle–syringe method. The inflation process by stepwise addition of the liquid to the droplet leads to the contact line advancing outwardly along the major axis with advancing angle (θ_a). Although the droplet width is constrained by the edge of the plane, the CA along the minor axis (θ_w) increases and its value is greater than θ_a (θ_w > θ_a). Deflation process by stepwise withdrawal of liquid from the droplet results in the contact line retracting inwardly along the major axis as the CA reduces to receding angle (θ_r). In the meantime, the CA along the minor axis decreases as well. Both advancing and receding angles acquired from the narrow rectangular plane are confirmed with those obtained form the typical large surface of acrylic glass. On the basis of free energy minimization and liquid-induced defects model, Surface Evolver simulations are performed to reproduce the behavior of droplet on the narrow rectangular plane during the inflation–deflation process. The results of experiment and simulation agree with each other very well.     

Dynamical force and imaging characterization of superhydrophobic surfaces

We devised a dangling cantilever optical lever setup with imaging that permits dynamical studies of superhydrophobic surfaces without the effects of gravitational acceleration for better insight into the mechanics. The setup enabled us to ascertain liquid loss and ascribe it to the interaction of liquid that just touched the superhydrophobic surface as it translated at various constant lateral speeds. At lower speeds (20-60 μm/s), the interactions were characterized by a strong initial liquid pin (at up to 0.6 nN force) and depin followed by a series of smaller force pin and depins before sufficient liquid loss led to total liquid detachment from the surface. At higher translation speeds (80-100 μm/s), the interactions were characterized by liquid pinning and depinning processes at a sustained force (around 0.7 nN) in which liquid loss was low enough to engender a much later liquid detachment (beyond 100 s). A linear reduction of the receding contact angle with time, but not with the advancing contact angle, was found up to the point of first liquid depinning. This suggested a stronger role played by the receding contact line in establishing liquid adherence to the superhydrophobic surface. The detachment process from the surface was also characterized by a liquid bridge driven to rupture by way of liquid being conveyed away from the bridge.     

Transport dynamics in open microfluidic grooves

In microscopic rectangular grooves various liquid wetting morphologies can be found, depending on the wettability and details of the geometry. When these morphologies are combined with a method to vary the apparent contact angle reversibly, transitions between droplike objects and elongated liquid filaments can be induced. Liquid can thus be transported on demand along the grooves. The dynamics of liquid filaments advancing into grooves as well as receding from grooves has been studied, varying the contact angle using the electrowetting effect. The dynamics of the receding filament is purely capillarity driven and depends only on the contact angle, the viscosity of the liquid, and the geometry of the groove. The length and the dynamics of the advancing filaments, on the other hand, are strongly dependent on the ionic content of the liquid and the applied ac voltage.     

Recent progress in experiments for sessile droplet wetting on structured surfaces

Wetting of a sessile droplet on structured or patterned surface can be found in a broad range of applications. The researchers have been promoted to keep working on the topic. The review is on the basis of the recent experimental advances on the sessile droplet wetting on the hydrophobic, hydrophilic, or combined hydrophobic and hydrophilic surfaces under isothermal conditions, and on heating or cooling substrates having nonisothermal conditions. More attention has been paid on the wetting configuration between the sessile droplet and the structured substrate; the research gap has been discussed on identifying the three-phase line shape. Further, the three-dimensional measurement for the sessile droplets on the patterned surfaces with focusing more on the contact line of sessile droplets might reveal new physical insights. This review targets at building a holistic overview on the sessile droplet wetting behaviors on the structured substrate in the past 2 years.     

Planar and non-planar solidification of optically organised smectic films

This letter describes an original freezing process that yields homogeneous solid films at ambient temperature with preservation of the layered structure of the chiral smectic phase. One of the most remarkable features of the process is its ability to provide complexly bent films with arbitrary three-dimensional shapes. Their optical homogeneity is observed in the planar as well as in the bent films. The method is very simple. After forming the films by spreading the liquid crystal above a hole in a glass slice placed over a hot stage, the film is heated from below. The hot film is exposed to ambient temperature. Then, a solid object at room temperature with a specifically adapted shape is immersed in the liquid film. The mechanical constraints imposed by the object curves the film and stabilises various solid two- and three-dimensional structures. Their homogeneous optical properties are due to long-range organisation of the molecular orientation (tilt), which combines with a complex helical arrangement of the frozen smectic layers.