Friction and Wetting Transitions of Magnetic Droplets on Micropillared Superhydrophobic Surfaces

Reliable characterization of wetting properties is essential for the development and optimization of superhydrophobic surfaces. Here, the dynamics of superhydrophobicity is studied including droplet friction and wetting transitions by using droplet oscillations on micropillared surfaces. Analyzing droplet oscillations by high‐speed camera makes it possible to obtain energy dissipation parameters such as contact angle hysteresis force and viscous damping coefficients, which indicate pinning and viscous losses, respectively. It is shown that the dissipative forces increase with increasing solid fraction and magnetic force. For 10 µm diameter pillars, the solid fraction range within which droplet oscillations are possible is between 0.97% and 2.18%. Beyond the upper limit, the oscillations become heavily damped due to high friction force. Below the lower limit, the droplet is no longer supported by the pillar tops and undergoes a Cassie–Wenzel transition. This transition is found to occur at lower pressure for a moving droplet than for a static droplet. The findings can help to optimize micropillared surfaces for low‐friction droplet transport.     

Solidification contact angles of molten droplets deposited on solid surfaces

Droplet impact and equilibrium contact angle have been extensively studied. However, solidification contact angle, which is the final contact angle formed by molten droplets impacting on cold surfaces, has never been a study focus. The formation of this type of contact angle was investigated by experimentally studying the deposition of micro-size droplets (∼39 μm in diameter) of molten wax ink on cold solid surfaces. Scanning Electron Microscope (SEM) was used to visualize dots formed by droplets impacted under various impact conditions, and parameters varied included droplet initial temperature, substrate temperature, flight distance of droplet, and type of substrate surface. It was found that the solidification contact angle was not single-valued for given droplet and substrate materials and substrate temperature, but was strongly dependent on the impact history of droplet. The angle decreased with increasing substrate and droplet temperatures. Smaller angles were formed on the surface with high wettability, and this wetting effect increased with increasing substrate temperature. Applying oil lubricant to solid surfaces could change solidification contact angle by affecting the local fluid dynamics near the contact line of spreading droplets. Assuming final shape as hemispheres did not give correct data of contact angles, since the final shape of deposited droplets significantly differs from a hemispherical shape.     

Surface Modification of Diamond‐Like Carbon Film with Polymer Brushes Using a Bio‐Inspired Catechol Anchor for Excellent Biological Lubrication

Diamond‐like carbon (DLC) film has emerged as a promising material for biomedical applications, but its low tribological properties in air could not be adapted in water and biological fluids. Herein, mussel‐inspired catechol adhesive is presented to functionalize DLC film and then polymer brushes are grafted by surface initiated atom transfer radical polymerization (SI‐ATRP) to mimic excellent biological lubrication of articular cartilage. Macroscopic tribological evaluation demonstrates low and stable friction coefficient of polymer brushe modified DLC film in water and biological fluids when sliding with a soft polydimethylsiloxane (PDMS) hemisphere, owing to viscous fluid‐like boundary lubricant film being formed by high hydration of polymer chains. The strong adhesive capability of catechol anchors also prevents polymer chains being sheared off from the substrate during friction tests. The friction responsiveness of PSPMA brushes is observed in electrolyte solution due to the conformation change of polymer chains. The successful functionalization of DLC with polymer brushes affords DLC film excellent biological lubrication and thus will broaden the scope of its applications in biomedical field.     

Molecular dynamics studies of microscopic wetting phenomena on self-assembled monolayers

Molecular dynamics calculations have been used to investigate the behavior of overlayers of water or n-alkane fluids on solid surfaces formed from “self-assembled” monolayers of long-chain hydrocarbons. A microscopic analog of the wetting contact angle is used to measure the surface wetting characteristics. On a nonpolar surface, formed by close packed chains having -CH₃ tailgroups, the water molecules aggregate to form a compact droplet. The calculated contact angle of the droplet is similar to experimental values for macroscopic water droplets. Contrary to intuition, the overlayers of hexadecane or decane form droplets with smaller contact angles on the same surface. However, the calculated contact angles are again in reasonable accord with experimental values.     

PDMS微/毫流控芯片的简易快速制备及其疏水性研究

将玻璃片/管、锡箔等材料进行组装、通道搭建制备出带有管路图案的容器,再将聚二甲基硅氧烷(PDMS)预聚体浇注到该容器中固化成型,之后通过模具拆卸、切割制备出整体式PDMS微/毫流控芯片.该法可获取各种微通道尺寸保真性好的整体式芯片,其通道截面圆形度与由热压法制备的微流控芯片相比有明显提高.另将获得的PDMS芯片经过30 min紫外改性后,其疏水性得到明显改善,与H2O的接触角由钝角变为了锐角,并在室温下静置能维持1 h左右的改性,完全能够满足液滴成型实验的时间要求.另外将该法制备的PDMS整体式芯片用于单分散液滴、双重液滴制备时,可在较宽的流速范围(4 mL/h~36 mL/h)内得到粒径可控的液滴,并且液滴在芯片通道中不易破乳,表现出良好的稳定性.这对于靶球制备、功能材料合成、活性成分保持等应用有重要意义.     

Anisotropy in wetting of oriented sapphire surfaces by liquid Al–Cu alloys

The coexistence of a liquid with a solid and a gas phase causes a contact angle at the triple line and results in a certain work of adhesion. These properties were studied for liquid Al, Cu, and their alloys on single-crystalline sapphire surfaces with C(0001)-, A(11-20)-, and R(1-102)- orientation. Measurements were performed at 1100 °C and under $3 \cdot 10^4\, \hbox{Pa}$ Ar atmosphere in a sessile drop apparatus. There, the sample was heated and melted separately from the substrate within a drop dispenser. Only after the desired measurement conditions were reached, the liquid metal was released. Depending on the alloy composition, the wetting angle approached a constant value within few minutes after the contact of droplet and substrate was established: For pure Cu the contact angle increased to an equilibrium value of 116° ± 5°, which is identical for all the studied sapphire surfaces. For pure Al an anisotropy of the contact angle with regard to these surfaces is found: time evolution of the Al contact angle is only observed for wetting of C-surfaces. Wetting of A- and R-surfaces shows no pronounced time dependence. In these cases, a smaller contact angle of about 90° is observed. Wetting of the different sapphire surfaces by Al–Cu alloys corresponds qualitatively to their wetting by pure Al: again, only for C-surfaces a time-dependent increase of the contact angle is observed. On A- and R-surfaces wetting is not time-dependent and the contact angle increases with Cu content of the alloy.     

Relaxation Dynamics of Non-Power-Law Fluids

The relaxation of non-Newtonian liquids with non-power-law rheology on partially wetted surfaces is rarely investigated. This study assesses the relaxation behavior of 14 partial wetting systems with non-power-law fluids by sessile drop method. These systems are two carboxymethylcellulose sodium solutions on two kinds of slides, cover glass, and silicon wafer surfaces; three polyethylene glycol (PEG400) + silica nanoparticle suspensions on polymethyl methacrylate and polystyrene surfaces. The dynamic contact angle and moving velocity of contact line relationship $(\theta _\mathrm{D}-U)$ data for relaxation drops of the 14 tested systems demonstrate a power-law fluid-like behavior, and the equivalent power exponent $n_\mathrm{e}$ for a certain fluid on different solid substrates are uniform. By analyzing the relationship between the equivalent power exponent and shear rate, it is proposed that a fluid regime with shear rates of a few tens of s $^{-1}$ controls relaxation dynamics.     

Drop detachment and motion on fuel cell electrode materials

Liquid water is pushed through flow channels of fuel cells, where one surface is a porous carbon electrode made up of carbon fibers. Water drops grow on the fibrous carbon surface in the gas flow channel. The drops adhere to the superficial fiber surfaces but exhibit little penetration into the voids between the fibers. The fibrous surfaces are hydrophobic, but there is a substantial threshold force necessary to initiate water drop motion. Once the water drops begin to move, however, the adhesive force decreases and drops move with minimal friction, similar to motion on superhydrophobic materials. We report here studies of water wetting and water drop motion on typical porous carbon materials (carbon paper and carbon cloth) employed in fuel cells. The static coefficient of friction on these textured surfaces is comparable to that for smooth Teflon. But the dynamic coefficient of friction is several orders of magnitude smaller on the textured surfaces than on smooth Teflon. Carbon cloth displays a much smaller static contact angle hysteresis than carbon paper due to its two-scale roughness. The dynamic contact angle hysteresis for carbon paper is greatly reduced compared to the static contact angle hysteresis. Enhanced dynamic hydrophobicity is suggested to result from the extent to which a dynamic contact line can track topological heterogeneities of the liquid/solid interface.     

Hydrophobicity, adhesion, and friction properties of nanopatterned polymers and scale dependence for micro- and nanoelectromechanical systems

Applications in micro/nanoelectromechanical systems generally require low adhesion and friction values between two materials of interest. By alteration of the material combinations and surface roughness, including nanopatterning, adhesion and friction can be tailored to meet a specific requirement. Surfaces found in nature, such as hydrophobic lotus leaves, provide a good example of this optimization. Recent models of hydrophobic leaf surfaces show a correlation between roughness and hydrophobicity, which can be mimicked by the presence of nanopatterned asperities on a polymer surface. In addition, by introducing nanopatterns on the polymer surface, the real area of contact decreases when another surface comes into contact with the patterned surface, which reduces adhesion and friction. This study explores the effect of nanopatterning on hydrophobicity, adhesion, and friction for two different hydrophilic polymers, poly(methyl methacrylate) (PMMA) and polyurethane acrylate (MINS), with two types of patterned asperities, low aspect ratio and high aspect ratio, investigated by use of an atomic/friction force microscope (AFM/FFM). In addition to the polymers, a hydrophobic coating was deposited on the surface of the patterned PMMA to study the effect of roughness on the contact angle, along with adhesion and friction. Relative contribution due to change in contact angle and real area of contact are explored. Scale dependence on adhesion and friction was also studied using AFM tips of various radii. Since applications of these surfaces will require operation in varying environments, the effect of relative humidity is investigated.     

接触角和质量分数对液滴冻结过程的影响

本文通过Fluent软件的凝固/熔化模型,模拟了接触角及质量分数对纯水和氯化钠溶液在冷表面冻结过程的影响,选择铜片为亲水表面,纳米膜表面为疏水表面,对液滴在不同表面特性条件下的冻结过程进行实验研究.结果表明:液滴在冷表面的冻结特性与接触角、质量分数有关.当溶液质量分数一定时,接触角越小,液滴冻结速度越快,完全冻结时间越...     

Heparin-containing block copolymers

Newly synthesized heparin-containing block copolymers, consisting of a hydrophobic block of polystyrene (PS), a hydrophilic spacer-block of poly(ethylene oxide) (PEO) and covalently bound heparin (Hep) as bioactive block, were coated on aluminium, glass, polydimethylsiloxane (PDMS), PS or Biomer substrates. Surfaces of coated materials were characterized by transmission electron microscopy (TEM), contact angle measurements and X-ray photoelectron spectroscopy for chemical analysis (XPS). It was demonstrated by TEM that thin films of PS-PEO and PS-PEO-Hep block copolymers consisted of heterogeneous microphase separated structures. Using sessile-drop and Wilhelmy plate dynamic contact angle measurements, insight was provided into the hydrophilicity of the surfaces of the coatings. Measurements with hydrated coatings of PS-PEO and PS-PEO-Hep block copolymers revealed that the surfaces became more hydrophilic during immersion in water, due to relaxation/reorientation, or swelling of PEO or PEO-Hep domains, respectively. XPS results for PS, PEO, heparin and PS-PEO as powder agreed well with qualitative and quantitative predictions. XPS results for films of PS-PEO and PS-PEO-Hep block copolymers showed enrichments of PEO in the top layers of the coatings. This effect was more pronounced for hydrated surfaces. Only small amounts of heparin were detected at the surface of coatings of PS-PEO-Hep block copolymers.     

类荷叶表面疏水结构的材料表面制备

利用纳米/微米复模成型的方法,制备了荷叶表面微乳突状疏水结构的聚乙烯醇(PVA)和聚苯乙烯(PS)阴模模具,并利用阴模复模成型在聚二甲基硅烷(PDMS)表面制备了类荷叶的表面结构.扫描电子显微镜(SEM)的观察表明PDMS材料表面上制得的类荷叶结构与荷叶表面的微乳突结构有较好的一致性,而PVA阴模在保持微观结构上更有优势.通过对水滴在PDMS材料表面接触角的测量,证明了在制备有类荷叶表面结构的PDMS材料表面上,水滴的接触角可以得到显著提高.     

Analysis of abnormal wear on a certain type of CRH380 high-speed railway grounding brush

This paper investigated the causes of premature wear of grounding brushes in high-speed train which was less than 40 % of design service life. The grounding brushes were analyzed from the material composition, microstructure and mechanical property under different wear conditions. The results indicated that their material composition and microstructure were basically identical, and the phase compositions of the four samples were mainly copper (Cu) and carbon (C). There were no obvious defects in the structure. The load differences will give rise to vibration of the friction pairs and lead to electrical erosion on the worn surface. The electrical erosion produced oxides and fused hard particles as well as caused abrasive wear. The test results also indicated that the spring-induced gap across the contact surfaces resulted in electrical erosion.     

Epitaxial growth of silicon whiskers without tapering at the base

Based on the measured parameters of the tapered portion (pedestal) at the base of silicon whiskers, we show that the tapering is the consequence of the increase in the contact angle of the liquid droplet and is due to the fact that the surface free energy of the three-phase system is constant (zero increment) during whisker growth. The growth angle of nanowhiskers should depend on their cross-sectional size because of the effect of the line tension at the three-phase boundary. A procedure is proposed for whisker growth without tapering at the base.     

Replication of surfaces of natural leaves for enhanced micro-scale tribological property

In this paper, we report on the replication of surfaces of Lotus and Colocasia leaves onto thin polymeric films using a capillarity-directed soft lithographic technique. The replication was carried out on poly(methyl methacrylate) (PMMA) film spin coated on silicon wafer using poly(dimethyl siloxane) (PDMS) molds. The friction properties of the replicated surfaces were investigated at micro-scale in comparison with those of PMMA thin film and uncoated silicon wafer. The coefficients of friction of the replicated surfaces were almost five times lower than those of the PMMA thin film and four times lower than those of the uncoated silicon wafer. The superior micro-tribological properties of the replicated surfaces could be attributed to the reduced real area of contact projected by the surfaces.     

Droplet on a fiber: geometrical shape and contact angle

Summary This paper is concerned with the geometrical shape, wetting length, and contact angle of a microdroplet on a fiber by using the method free energy variation. The governing equation and relevant boundary conditions of the microdroplet were re-derived based on the free energy variation of the droplet/fiber system. The geometrical shape of the droplet was determined as the combination of Legendre's elliptical functions of the first and second kinds, corresponding to the previous results in literature [6]. For contact angle θ >15°, a novel efficient semi-analytic approach was proposed to extract the contact angle from experimental data. The given approach can be used as theoretical basis of determining surface tension of fluids based on a sessile drop on a fiber.     

Physical ageing of the contact line on colloidal particles at liquid interfaces

Young's law predicts that a colloidal sphere in equilibrium with a liquid interface will straddle the two fluids, its height above the interface defined by an equilibrium contact angle. This has been used to explain why colloids often bind to liquid interfaces, and has been exploited in emulsification, water purification, mineral recovery, encapsulation and the making of nanostructured materials. However, little is known about the dynamics of binding. Here we show that the adsorption of polystyrene microspheres to a water/oil interface is characterized by a sudden breach and an unexpectedly slow relaxation. The relaxation appears logarithmic in time, indicating that complete equilibration may take months. Surprisingly, viscous dissipation appears to play little role. Instead, the observed dynamics, which bear strong resemblance to ageing in glassy systems, agree well with a model describing activated hopping of the contact line over nanoscale surface heterogeneities. These results may provide clues to longstanding questions on colloidal interactions at an interface.     

Solution-phase surface modification in intact poly(dimethylsiloxane) microfluidic channels

An improved approach composed of an oxidation reaction in acidic H2O2 solution and a sequential silanization reaction using neat silane reagents for surface modification of poly(dimethylsiloxane) (PDMS) substrates was developed. This solution-phase approach is simple and convenient for some routine analytical applications in chemistry and biology laboratories and is designed for intact PDMS-based microfluidic devices, with no device postassembly required. Using this improved approach, two different functional groups, poly(ethylene glycol) (PEG) and amine (NH2), were introduced onto PDMS surfaces for passivation of nonspecific protein absorption and attachment of biomolecules, respectively. X-ray electron spectroscopy and temporal contact angle experiments were employed to monitor functional group transformation and dynamic characteristics of the PEG-grafted PDMS substrates; fluorescent protein solutions were introduced into the PEG-grafted PDMS microchannels to test their protein repelling characteristics. These analytical data indicate that the PEG-grafted PDMS surfaces exhibit improved short-term surface dynamics and robust long-term stability. The amino-grafted PDMS microchannels are also relatively stable and can be further activated for modifications with peptide, DNA, and protein on the surfaces of microfluidic channels. The resulting biomolecule-grafted PDMS microchannels can be utilized for cell immobilization and incubation, semiquantitative DNA hybridization, and immunoassay.     

Superhydrophobic surfaces with hierarchical structure

The physics related to superhydrophobic surfaces has been investigated with attention of its potential applications in a variety of industrial and research fields. In the present study, we report a facile method for preparing superhydrophobic surfaces based on micro and nano scaled structures. Composite thin films are formed by using SiO₂ nanoparticles and poly(dimethylsiloxane) (PDMS). The static contact angle, advancing contact angle, and receding contact angle are measured to investigate the surfaces' water repelling property. The formed SiO₂-PDMS composite films, with different nanoparticle concentrations and sizes, can render the surfaces with superhydrophobicicty, exhibiting large contact angles and small contact angle hysteresis. The composite films are observed by using the Scanning Electron Microscope (SEM). It is demonstrated that the hierarchical structure in micro and nano scale on the surface, plays an important role in prompting the superhydrophobic (water-repelling) properties. Wetting phenomena and related theories are also discussed within the paper.     

Fabrication of polyethylene surface with stable superhydrophobicity by nanoparticle assisted thermal micromolding process

Superhydrophobic surface with lotus leaf effect has many practical and potential applications in different fields. In this paper, a novel process based on nanoparticle assisted thermal micromolding was developed to create polyethylene superhydrophobic surface. Briefly, a thin layer of TiO2 nanoparticles was first coated on the featured surface of the poly(dimethylsiloxane) (PDMS) stamp replicated from a fresh lotus leaf. Then low-density polyethylene (LDPE) was thermally pressed onto such TiO2 coated stamp. A control process was also performed by thermally pressing TiO2/LDPE nanocomposite material onto a blank PDMS stamp. Scanning electron microscopy (SEM) imaging and contact angle measurements showed that the surfaces of LDPE films replicated from stamp coated with TiO2 had more delicate nano-structures and higher water contact angles (> or = 155 degrees) than those replicated from the blank stamp. Moreover, the superhydrophobic surface formed by TiO2 assisted micromolding was relatively stable under water stream with high pressure. This study shows that nanoparticle assisted micromolding is an alternative technique to other techniques for large scale production of superhydrophobic polymeric films.