Carbon electrode obtained via pyrolysis of plasma-deposited parylene-C for electrochemical immunoassays.

In this study, parylene-C films from plasma deposition as well as thermal deposition were pyrolyzed to prepare a carbon electrode for application in electrochemical immunoassays. Plasma deposition could prepare parylene-C in a faster deposition rate and more precise control over the thickness in comparison with the conventional thermal deposition. To analyze the influence of the deposition method, the crystal and electronic structures of the pyrolyzed parylene-C films obtained via both deposition methods were compared using Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. For application as a carbon electrode in immunoassays, the electrochemical properties of the pyrolyzed carbon films from two both deposition methods were analyzed, including the double layer capacitance (2.10 µF cm-2 for plasma deposition and 2.20 µF cm-2 for thermal deposition), the apparent electron transfer rate (approximately 1.1 × 10-3 cm s-1 for both methods), and the electrochemical window (approximately -1.0 ∼ 2.1 V for both methods). Finally, the applicability of the pyrolyzed carbon electrode from parylene-C was demonstrated for the diagnosis of human hepatitis-C using various amperometric methods, such as cyclic voltammetry, chronoamperometry, square-wave voltammetry and differential pulse voltammetry.

Pixelated Microsized Quantum Dot Arrays Using Surface-Tension-Induced Flow.

Quantum dots (QDs) are semiconducting nanoparticles that exhibit unique fluorescent characteristics when excited by an ultraviolet light source. Owing to their highly saturated emissions, display panels using QDs as pixels have been presented. However, the complications of the nanofabrication procedure limit the industrial application of QDs. This study suggests a method to arrange high-aspect-ratio QD pixels by inducing both Laplace-pressure-driven capillary flow and thermally driven Marangoni flow. The evaporation of colloidal QDs induces a capillary flow that drives the QDs toward the inner tips of V-shaped structures. Additionally, the Marangoni flow arranges the gathered QDs at the tip; thus, they could form a high dune, overcoming the limitations of the existing capillary assembly method using evaporation. Using these phenomena, clover-shaped (assembly of V-shaped edges) templates were made to gather numerous QDs, and the clover with a 30° angle afforded the highest brightness among all the angle structures. Finally, by demonstrating a 100-cm2-sized QD microarray with high uniformity (98.6%), our method shows the feasibility of large-area fabrication, which has extensive application in manufacturing QD displays, anti-counterfeiting labels, and other QD-based optical devices.

Advanced Boiling-A Scalable Strategy for Self-Assembled Three-Dimensional Graphene.

Currently, researchers are paying much attention to the development of effective 3D graphene for applications in energy storage and environmental purification. Before commercialization, however, it is necessary to develop a method that allows for the large-scale production of such materials and enables good control over their structural and chemical properties. With this objective, we herein developed a simple method for the formation of large-scale (4 in. wafer) 3D graphene networks via the self-assembly of graphene sheets at a superheated liquid-vapor interface. The structural morphology of this porous network could be modified by controlling the vaporization rate, surface temperature of the target substrate, and amount of discharged colloids. The key mechanism behind this intriguing result was investigated by high-speed visualization of microdroplet behavior and extensive thermal analysis. This self-assembled 3D graphene had excellent electrical and mechanical properties. Our approach can be directly used for the mass production of graphene-based materials.

Pressure Drop with Moving Contact Lines and Dynamic Contact Angles in a Hydrophobic Round Minichannel: Visualization via Synchrotron X-ray Imaging and Verification of Experimental Correlations.

In hydrophobic mini- and microchannels, slug flow with moving contact lines is typically generated under various two-phase flow conditions. There is a significant pressure drop in this flow pattern with moving contact lines, which is closely related to the dynamic contact angles. Researchers have investigated dynamic contact angles experimentally for decades, but due to the limitations of visualization techniques, these experiments have typically been conducted in low Weber number regions (We < 10-3). In this study, we clearly visualized the dynamic contact angles of a liquid slug in high Weber number regions (10-3 < We <1) via synchrotron X-ray imaging with high temporal (∼1000 fps) and spatial (∼2 µm/pixel) resolutions. We precisely measured the pressure drop with moving contact lines in a hydrophobic minichannel (inner diameter = 1.018 mm). On the basis of our experimental data, we verified previous correlations for dynamic contact angles and explored the relationship between pressure drop with moving contact lines and dynamic contact angles.

Evaporation-Crystallization Method to Promote Coalescence-Induced Jumping on Superhydrophobic Surfaces.

Biphilic surfaces exhibit outstanding condensation efficiency compared to surfaces having homogeneous wettability. Especially, hydrophilic patterns on a superhydrophobic substrate significantly promote the coalescence-induced jumping of condensed droplets by increasing the nucleation rate of condensation, thus enhancing the condensation efficiency drastically. However, the application of biphilic surfaces in practical industries remains challenging because controlling the size and spacing of the hydrophilic spots on large and complex surfaces is difficult. In this study, we have achieved heterogeneous wettability using the evaporation-crystallization method, which can be applied to various surfaces as required by industries. The crystals generated using the evaporation-crystallization process drastically increased the number density of condensed droplets on a superhydrophobic surface (SHS), so the developed biphilic surface increased the cumulative volume of jumping droplets by up to 63% compared to that on a conventional superhydrophobic surface. Furthermore, the condensation dynamics on the biphilic surface were analyzed with the classical nucleation theory and the Ohnesorge number. The analysis results indicated that the generated hydrophilic crystals can reduce the nucleation energy barrier and decrease the available excessive surface energy of coalesced droplets on the biphilic surface; this implies that the size distribution of the crystals determines the condensation dynamics. In sum, this study not only introduced an effective surface tailoring approach for enhancing condensation but also provided insights into the design of optimum biphilic surfaces for various conditions, creating new opportunities to widen the applicability of biphilic surfaces in practical industries that exploit condensation.

Nanograssed Zigzag Structures To Promote Coalescence-Induced Droplet Jumping.

To increase the efficiency of jumping-droplet condensation, this study proposes a hierarchical superhydrophobic surface that promotes coalescence-induced jumping. Inspired by the phenomenon in which a growing droplet moves spontaneously within a superhydrophobic V structure, we fabricated nanograssed zigzag structures on the surface to induce the spontaneous motion of condensed droplets. The direction of the motion was parallel to the surface, so the condensed droplets easily coalesced on it. Compared with a conventional nanograssed superhydrophobic surface, the proposed surface increased the frequency of coalescence-induced jumping by ≥17 times and increased the cumulative volume of jumping droplets by ∼1.8 times. The proposed surface has great potential to increase the efficiency of applications such as water- and energy-harvesting and cooling systems that exploit jumping-droplet condensation.

Direct Visualization of the Behavior and Shapes of the Nanoscale Menisci of an Evaporating Water Droplet on a Hydrophilic Nanotextured Surface via High-Resolution Synchrotron X-ray Imaging.

Despite considerable research interest due to omnipresent and practical importance of interfacial phenomena (e.g., wetting and dewetting) on nanotextured surfaces in the academic and industrial fields, direct visualization of the behavior and shapes of liquid-vapor interfaces between nanoscale structures remains an arduous task because of the resolution limitations of visualization techniques. In this study, we succeeded in a first-hand visualization of the behavior and shapes of the liquid-vapor interfaces of a water droplet between nanometer-scale pillar during evaporation by introducing a synchrotron X-ray imaging technique with spatially high resolution (40 nm/a pixel). On the basis of the visualization data, we intensively analyzed and discussed the spreading and evaporation phenomena of a liquid droplet on hydrophilic nanotextured surfaces.

Wetting Criteria of Intrinsic Contact Angle To Distinguish between Hydrophilic and Hydrophobic Micro-/Nanotextured Surfaces: Experimental and Theoretical Analysis with Synchrotron X-ray Imaging.

In this study, the existing knowledge on the wetting criterion, that is, the intrinsic contact angle, for distinguishing between hydrophilic and hydrophobic textured surfaces is verified experimentally. A precise apparent contact angle is measured on micro-, nano-, and micro-/nanotextured surfaces to quantitatively define the surface-wetting conditions. In particular, X-ray tomography is introduced to measure precise geometric morphologies of nano- and micro-/nanotextured surfaces, and the wetting state of the textured surfaces is clearly visualized using synchrotron X-ray imaging. By comparing previous theoretical models and experimental results, it is verified that the intrinsic contact angle for distinguishing between hydrophilic and hydrophobic textured surfaces should be corrected from 90° to 43°. In addition, nonwetting phenomena in the region of the intrinsic contact angle between 43° and 90° are discussed.

Effects of wettability on droplet movement in a V-shaped groove.

As basic research to understand the behavior of droplets on structured surfaces, we investigated droplet movement in a V-shaped groove while the volume of the droplet changes. We developed a model to explain the mechanism of the droplet movement and the effects of the wettability of the inner walls of the groove on the droplet movement. Furthermore, the model predicted new phenomena and explains the effect of the nonhomogeneous wettability on droplet movement. The predictions of the model match the experimental results well. This research can provide the basic knowledge for manipulating droplets with structured surfaces for various applications.

Synchrotron x-ray imaging visualization study of capillary-induced flow and critical heat flux on surfaces with engineered micropillars.

Over the last several decades, phenomena related to critical heat flux (CHF) on structured surfaces have received a large amount of attention from the research community. The purpose of such research has been to enhance the safety and efficiency of a variety of thermal systems. A number of theories have been put forward to explain the key CHF enhancement mechanisms on structured surfaces. However, these theories have not been confirmed experimentally because of limitations in the available visualization techniques and the complexity of the phenomena. To overcome these limitations and elucidate the CHF enhancement mechanism on the structured surfaces, we introduce synchrotron x-ray imaging with high spatial (~2 µm) and temporal (~20,000 Hz) resolutions. This technique has enabled us to confirm that capillary-induced flow is the key CHF enhancement mechanism on structured surfaces.

Loss of superhydrophobicity of hydrophobic micro/nano structures during condensation.

Condensed liquid behavior on hydrophobic micro/nano-structured surfaces is a subject with multiple practical applications, but remains poorly understood. In particular, the loss of superhydrophobicity of hydrophobic micro/nanostructures during condensation, even when the same surface shows water-repellant characteristics when exposed to air, requires intensive investigation to improve and apply our understanding of the fundamental physics of condensation. Here, we postulate the criterion required for condensation to form from inside the surface structures by examining the grand potentials of a condensation system, including the properties of the condensed liquid and the conditions required for condensation. The results imply that the same hydrophobic micro/nano-structured surface could exhibit different liquid droplet behavior depending on the conditions. Our findings are supported by the observed phenomena: the initiation of a condensed droplet from inside a hydrophobic cavity, the apparent wetted state changes, and the presence of sticky condensed droplets on the hydrophobic micro/nano-structured surface.

Dynamics of contact line depinning during droplet evaporation based on thermodynamics.

For several decades, evaporation phenomena have been intensively investigated for a broad range of applications. However, the dynamics of contact line depinning during droplet evaporation has only been inductively inferred on the basis of experimental data and remains unclear. This study focuses on the dynamics of contact line depinning during droplet evaporation based on thermodynamics. Considering the decrease in the Gibbs free energy of a system with different evaporation modes, a theoretical model was developed to estimate the receding contact angle during contact line depinning as a function of surface conditions. Comparison of experimentally measured and theoretically modeled receding contact angles indicated that the dynamics of contact line depinning during droplet evaporation was caused by the most favorable thermodynamic process encountered during constant contact radius (CCR mode) and constant contact angle (CCA mode) evaporation to rapidly reach an equilibrium state during droplet evaporation.

Enhanced heat transfer is dependent on thickness of graphene films: the heat dissipation during boiling.

Boiling heat transfer (BHT) is a particularly efficient heat transport method because of the latent heat associated with the process. However, the efficiency of BHT decreases significantly with increasing wall temperature when the critical heat flux (CHF) is reached. Graphene has received much recent research attention for applications in thermal engineering due to its large thermal conductivity. In this study, graphene films of various thicknesses were deposited on a heated surface, and enhancements of BHT and CHF were investigated via pool-boiling experiments. In contrast to the well-known surface effects, including improved wettability and liquid spreading due to micron- and nanometer-scale structures, nanometer-scale folded edges of graphene films provided a clue of BHT improvement and only the thermal conductivity of the graphene layer could explain the dependence of the CHF on the thickness. The large thermal conductivity of the graphene films inhibited the formation of hot spots, thereby increasing the CHF. Finally, the provided empirical model could be suitable for prediction of CHF.

A novel role of three dimensional graphene foam to prevent heater failure during boiling.

We report a novel boiling heat transfer (NBHT) in reduced graphene oxide (RGO) suspended in water (RGO colloid) near critical heat flux (CHF), which is traditionally the dangerous limitation of nucleate boiling heat transfer because of heater failure. When the heat flux reaches the maximum value (CHF) in RGO colloid pool boiling, the wall temperature increases gradually and slowly with an almost constant heat flux, contrary to the rapid wall temperature increase found during water pool boiling. The gained time by NBHT would provide the safer margin of the heat transfer and the amazing impact on the thermal system as the first report of graphene application. In addition, the CHF and boiling heat transfer performance also increase. This novel boiling phenomenon can effectively prevent heater failure because of the role played by the self-assembled three-dimensional foam-like graphene network (SFG).

Self-assembled foam-like graphene networks formed through nucleate boiling.

Self-assembled foam-like graphene (SFG) structures were formed using a simple nucleate boiling method, which is governed by the dynamics of bubble generation and departure in the graphene colloid solution. The conductivity and sheet resistance of the calcined (400°C) SFG film were 11.8 S·cm(-1) and 91.2 Ω□(-1), respectively, and were comparable to those of graphene obtained by chemical vapor deposition (CVD) (~10 S·cm(-1)). The SFG structures can be directly formed on any substrate, including transparent conductive oxide (TCO) glasses, metals, bare glasses, and flexible polymers. As a potential application, SFG formed on fluorine-doped tin oxide (FTO) exhibited a slightly better overall efficiency (3.6%) than a conventional gold electrode (3.4%) as a cathode of quantum dot sensitized solar cells (QDSSCs).

Drop impact characteristics and structure effects of hydrophobic surfaces with micro- and/or nanoscaled structures.

We report the drop impact characteristics on four hydrophobic surfaces with different well-scale structures (smooth, nano, micro, and hierarchical micro/nano) and the effects of those structures on the behavior of water drops during impact. The specimens were fabricated using silicon wet etching, black silicon formation, or the combination of these methods. On the surfaces, the microstructures form obstacles to drop spreading and retracting, the nanostructures give extreme water-repellency, and the hierarchical micro/nanostructures facilitate drop fragmentation. The maximum spreading factor (D*(max)) differed among the structures. On the basis of published models of D*(max), we interpret the results of our experiment and suggest reasonable explanations for these differences. Especially, the micro/nanostructures caused instability of the interface between liquid and air at Weber number We > ~80 and impacting drops fragmented at We > ~150.

Nucleate boiling performance on nano/microstructures with different wetting surfaces.

A study of nucleate boiling phenomena on nano/microstructures is a very basic and useful study with a view to the potential application of modified surfaces as heating surfaces in a number of fields. We present a detailed study of boiling experiments on fabricated nano/microstructured surfaces used as heating surfaces under atmospheric conditions, employing identical nanostructures with two different wettabilities (silicon-oxidized and Teflon-coated). Consequently, enhancements of both boiling heat transfer (BHT) and critical heat flux (CHF) are demonstrated in the nano/microstructures, independent of their wettability. However, the increment of BHT and CHF on each of the different wetting surfaces depended on the wetting characteristics of heating surfaces. The effect of water penetration in the surface structures by capillary phenomena is suggested as a plausible mechanism for the enhanced CHF on the nano/microstructures regardless of the wettability of the surfaces in atmospheric condition. This is supported by comparing bubble shapes generated in actual boiling experiments and dynamic contact angles under atmospheric conditions on Teflon-coated nano/microstructured surfaces.

Wicking and spreading of water droplets on nanotubes.

Recently, there has been intensive research on the use of nanotechnology to improve the wettability of solid surfaces. It is well-known that nanostructures can improve the wettability of a surface, and this is a very important safety consideration in regard to the occurrence of boiling crises during two-phase heat transfer, especially in the operation of nuclear power plant systems. Accordingly, there is considerable interest in wetting phenomena on nanostructures in the field of nuclear heat transfer. Much of the latest research on liquid absorption on a surface with nanostructures indicates that liquid spreading is generated by capillary wicking. However, there has been comparatively little research on how capillary forces affect liquid spreading on a surface with nanotubes. In this paper, we present a visualization of liquid spreading on a zircaloy surface with nanotubes, and establish a simple quantitative method for measuring the amount of water absorbed by the nanotubes. We successfully describe liquid spreading on a two-dimensional surface via one-dimensional analysis. As a result, we are able to postulate a relationship between liquid spreading and capillary wicking in the nanotubes.

One step immobilization of peptides and proteins by using modified parylene with formyl groups.

One-step immobilization method for peptides and proteins is developed by using modified parylene film with formyl groups which is suitable for microplate-based immunoassay and SPR biosensor application. The immobilization of peptides and proteins is achieved through the covalent bonding of the formyl group with the primary amine groups of peptides and proteins, which no additional activation step is required. In this work, the immobilization efficiency of parylene-H is estimated in comparison with parylene-A and physical adsorption, using biotinylated-cyclic citrullinated peptide (biotinylated-CCP), human chorionic gonadotropin (hCG) and horseradish peroxidase (HRP) as model proteins. The applicability of parylene-H film to SPR biosensor is demonstrated by estimating the detection range and sensitivity of SPR biosensor at various thicknesses. The immobilization efficiency of parylene-H film for SPR biosensor was compared with physical adsorption by using HRP as a model protein.

Parylene-A coated microplate for covalent immobilization of proteins and peptides.

Various types of microplates made of polystyrene have been widely used for immunoassays. A new microplate suitable for the covalent immobilization of proteins and peptides was developed by thermal deposition of amino-modified parylene (parylene-A) on the microplate. The primary amine groups of the parylene-A was exploited for the covalent coupling of proteins and peptides. The optical transmittance at the wavelength of 400-500 nm was estimated to be suitable for the application to immunoassays. The immobilization efficiency of the parylene-A coated microplate was demonstrated to be far improved in comparison to the conventional microplate by using horseradish peroxidase (HRP), anti-HRP antibody and a peptide with 9-residues as model biomolecules.