Contact Angle Measurement for Dispersed Microspheres Using Scanning Confocal Microscopy

Abstract

Scanning confocal microscopy was used for contact angle measurement of individual microspheres. The measurements were carried out by using different laser‐scanned layers of the particle floating on the air–water interface. The ratio of the diameter for the cross‐section of the protruded area of the particle at the air–water interface to the actual diameter of the particle is used for contact angle measurements. Two systems, i.e., glass and polystyrene microspheres with diameters of 3–10 and 6 µm, respectively, with water were used for this investigation (this size range of particles are most relevant to inhalation applications). Using the developed methodology, contact angles of 27° and 41° were measured (with water) for glass and polystyrene particles, respectively. The theoretical error in contact angle measurement for the developed methodology is determined to be generally about 1° with a maximum of 3° for contact angle of particles ranging from 2 to 24 µm in size; the experimental error was 4–6°. The contact angles of glass and polystyrene particles were compared to those obtained from pendant drop method and confirmed.     

Switching and structuring of binary reactive polymer brush layers

Switchable binary polymer brushes grafted to Si-wafers were prepared from hydrophilic and hydrophobic polymer components. When exposed to solvents, either the hydrophobic or the hydrophilic component extends in to the liquid phase, depending on the polarity of the solvent. The hydrophilic component was poly-2-vinylpyridine; the hydrophobic component was made photocrosslinkable in that a polystyrene copolymer containing a photodimerizing chromophore was used. In this system surfaces differing in water contact angle between 60° and 100° can be produced by variation of the solvent. The chromophore was phenylindene, which forms crosslinks upon direct UV-irradiation. Therefore, the polystyrene component can be fixed in the extended or collapsed state. It will be shown that by irradiation through an appropriate mask, surfaces can be structured and the structures fixed. In both the systems structural patterns differing in surface properties were produced and fixed photochemically.     

Superhydrophobic surface fabricated by modifying silica coated multiwalled carbon nanotubes composites

A superhydrophobic surface with maximum static water contact angle of 156° and sliding angle of 3.5° was fabricated by modifying the silica coated multiwalled carbon nanotube composites (SiO₂/MWCNTs) using a silane coupling agent vinyltriethoxysilane. The structures of SiO₂/MWCNTs and superhydrophobic surface were investigated by infrared spectrometer and transmission electron microscopy. The results indicated that silica had been successfully grafted onto MWCNTs and the SiO₂/MWCNTs had been chemical modified by vinyl triethoxy successfully. The morphology of our prepared superhydrophobic surface, investigated by scanning electron microscopy, showed a characteristic rough structure. The effects of pH value and exposure time on the stability of the superhydrophobic surface were also investigated. The superhydrophobic film shows reliable acid and alkali resistance and aging resistance, indicating that it will have a wide range of applications.     

Surface modification of polymers. I. Vapour phase photografting with acrylic acid

Surfaces of low density polyethylene, high density polyethylene, and polystyrene have been modified by grafting with acrylic acid. Benzophenone and acrylic acid in the vapor phase were UV-irradiated in the presence of a polymer substrate. Grafting with acrylic acid took place in a thin layer on the surface, thus increasing the wettability of the polymer. After 5 min of irradiation, the contact angle against water had decreased to 20° for polystyrene and 50° for the polyethylene samples. ESCA measurements on samples irradiated for 5 min showed a 90% poly(acrylic acid) coverage of the surface for polystyrene, 63% for low density polyethylene, and 56% for high density polyethylene. Acetone or ethanol were used as carriers of monomer and initiator. Acetone was able to initiate grafting and was found to promote and direct grafting to the surface. The stability of the acrylic acid grafted surfaces was studied by contact angle measurements and ESCA. At room temperature, the grafted layer is confined to the surface, but when the material was heated in air the surface was reshaped into a hydrophobic one. The process was reversible. In aqueous surroundings at elevated temperatures the hydrophilic character of the surface was restored.     

以砂纸为模板制作聚合物超疏水表面

报道了一种聚合物材料超疏水表面的简便制备方法. 以不同型号的金相砂纸为模板, 通过浇注成型或热压成型技术, 在聚合物表面形成不同粗糙度的结构. 接触角实验结果证明, 聚合物表面与水的接触角随着所用砂纸模板粗糙度的增加而加大, 其中粒度号为W7和W5砂纸制作的表面与水的接触角可超过150°, 显示出超疏水性质. 多种聚合物使用砂纸为模均可制备不同粗糙度及超疏水的表面, 本征接触角对复制表面浸润性的影响从Wenzel态到Cassie态而变小. 扫描电镜结果表明, 不规则形状的砂纸磨料颗粒构成了超疏水所需要的微纳米结构的模板.     

Cell adhesion and surface properties of polystyrene surfaces grafted with poly(N-isopropylacrylamide)

Cell adhesion plays a key role in various aspects of biological and medical sciences. In this study, poly(Nisopropylacrylamide) (PNIPAM) was grafted on polystyrene surfaces using different solvents under UV radiation. Moreover, the relation between surface roughness and cell adhesion were evaluated by gravimetric, SEM, AFM, contact angle measurement and cellular analyses. The gravimetric analysis clearly indicated an increase in the grafting by adding 10% methanol to water. The study of surface topography by AFM images showed an increase in the surface roughness and as a result of which, a decrease in wettablity was observed. At 37 °C, epithelial cells were well attached and proliferated on the grafted surfaces, while these cells were spontaneously detached below 32 °C in the absence of any enzymes. Moreover, MTT assay and SEM images indicated good cell viability and an increase in cell adhesion caused by the roughness increase. The results of this study reveal the great potential of PNIPAM-grafted polystyrene for being used in the biomedical fields such as drug delivery systems, tissue engineering and cell separation.     

Creation of “Rose Petal” and “Lotus Leaf” Effects on Alumina by Surface Functionalization and Metal‐Ion Coordination

Functional differences between superhydrophobic surfaces, such as lotus leaf and rose petals, are due to the subtle architectural features created by nature. Mimicry of these surfaces with synthetic molecules continues to be fascinating as well as challenging. Herein, we demonstrate how inherently hydrophilic alumina surface can be modified to give two distinct superhydrophobic behaviors. Functionalization of alumina with an organic ligand resulted in a rose‐petal‐like surface (water pinning) with a contact angle of 145° and a high contact angle hysteresis (±69°). Subsequent interaction of the ligand with Zn²⁺ resulted in a lotus‐leaf‐like surface with water rolling behavior owing to high contact angle (165°) and low‐contact‐angle‐hysteresis (±2°). In both cases, coating of an aromatic bis‐aldehyde with alkoxy chain substituents was necessary to emulate the nanowaxy cuticular feature of natural superhydrophobic materials.     

A facial approach to fabricate superhydrophobic aluminum surface

A facial chemical etching method was developed for fabricating superhydrophobic aluminum surfaces. The resultant surfaces were characterized by scanning electron microscopy, water contact angle (WCA) measurement, and optical methods. The surfaces of the modified aluminum substrates exhibit superhydrophobicity, with a WCA of 154.8° ± 1.6° and a water sliding angle of about 5°. The etched surfaces have binary structure consisting of the irregular microscale plateaus and caves in which there are the nanoscale block‐like convexes and hollows. The superhydrophobicity of aluminum substrates occurs only in some structures in which the plateaus and caves are appropriately ordered. The resulted surfaces have good self‐cleaning properties. The results demonstrate that it is possible to construct superhydrophobic surface on hydrophilic substrates by tailoring the surface structure to providing more spaces to trap air. Copyright © 2009 John Wiley & Sons, Ltd.     

Effects of contact angle hysteresis on ice adhesion and growth on superhydrophobic surfaces under dynamic flow conditions

In this paper, the icephobic properties of superhydrophobic surfaces are investigated under dynamic flow conditions using a closed-loop low-temperature wind tunnel. Superhydrophobic surfaces were prepared by coating aluminum and steel substrate plates with nano-structured hydrophobic particles. The superhydrophobic plates, along with uncoated controls, were exposed to a wind tunnel air flow of 12 m/s and ?7 °C with deviations of ±1 m/s and ±2.5 °C, respectively, containing micrometer-sized (～50 μm in diameter) water droplets. The ice formation and accretion were observed by CCD cameras. Results show that the superhydrophobic coatings significantly delay ice formation and accretion even under the dynamic flow condition of highly energetic impingement of accelerated supercooled water droplets. It is found that there is a time scale for this phenomenon (delay in ice formation) which has a clear correlation with contact angle hysteresis and the length scale of the surface roughness of the superhydrophobic surface samples, being the highest for the plate with the lowest contact angle hysteresis and finest surface roughness. The results suggest that the key for designing icephobic surfaces under the hydrodynamic pressure of impinging droplets is to retain a non-wetting superhydrophobic state with low contact angle hysteresis, rather than to only have a high apparent contact angle (conventionally referred to as a “static” contact angle).     

Nanoparticle flotation collectors II: the role of nanoparticle hydrophobicity

The ability of polystyrene nanoparticles to facilitate the froth flotation of glass beads was correlated to the hydrophobicity of the nanoparticles. Contact angle measurements were used to probe the hydrophobicity of hydrophilic glass surfaces decorated with hydrophobic nanoparticles. Both sessile water drop advancing angles, θ(a), and attached air bubble receding angle measurements, θ(r), were performed. For glass surfaces saturated with adsorbed nanoparticles, flotation recovery, a measure of flotation efficiency, increased with increasing values of each type of contact angle. As expected, the advancing water contact angle on nanoparticle-decorated, dry glass surfaces increased with surface coverage, the area fraction of glass covered with nanoparticles. However, the nanoparticles were far more effective at raising the contact angle than the Cassie-Baxter prediction, suggesting that with higher nanoparticle coverages the water did not completely wet the glass surfaces between the nanoparticles. A series of polystyrene nanoparticles was prepared to cover a range of surface energies. Water contact angle measurements, θ(np), on smooth polymer films formed from organic solutions of dissolved nanoparticles were used to rank the nanoparticles in terms of hydrophobicity. Glass spheres were saturated with adsorbed nanoparticles and were isolated by flotation. The minimum nanoparticle water contact angle to give high flotation recovery was in the range of 51° < θ(np(min)) ≤ 85°.     

Hydrophobic and Oleophobic Epoxy Surfaces Prepared by a Facile Process with Fluorosilicone Copolymer and SiO2 Nano-Particle

Hydrophobic and oleophobic surfaces with multi-scale structures were prepared on epoxy coating surfaces by using a facile process with fluorosilicone copolymer and SiO₂ nano-particles. The fluorosilicone copolymers were synthesized using perfluoroalkyl acrylate (FA), vinyltriethoxysilane (VTES) and styrene (St) as comonomers via radical emulsion polymerization. In this paper, the surface properties of epoxy coating modified by fluorosilicone copolymer and SiO₂ nano-particles were analyzed by using the contact angle measurement. The results showed that the modified epoxy coating surface exhibited not only excellent hydrophobicity but also oleophobicity, the water contact angle reached as high as 149° and the oil (atoleine) contact angle 101°, respectively.     

Condensation-induced wetting state and contact angle hysteresis on superhydrophobic lotus leaves

In this paper, we demonstrate how condensed moisture droplets wet classical superhydrophobic lotus leaf surfaces and analyze the mechanism that causes the increase of contact angle hysteresis. Superhydrophobic lotus leaves in nature show amazing self-cleaning property with high water contact angle (>150°) and low contact angle hysteresis (usually <10°), causing droplets to roll off at low inclination angles, in accordance with classical Cassie–Baxter wetting state. However, when superhydrophobic lotus leaves are wetted with condensation, the condensed water droplets are sticky and exhibit higher contact angle hysteresis (40–50°). Compared with a fully wetted sessile droplet (classical Wenzel state) on the lotus leaves, the condensed water droplet still has relatively large contact angle (>145°), suggesting that the wetting state deviates from a fully wetted Wenzel state. When the condensed water droplets are subjected to evaporation at room conditions, a thin water film is observed bridging over the micropillar structures of the lotus leaves. This causes the dew to stick to the surface. This result suggests that the condensed moisture does not uniformly wet the superhydrophobic lotus leaf surfaces. Instead, there occurs a mixed wetting state, between classical Cassie–Baxter and Wenzel states that causes a distinct increase of contact angle hysteresis. It is also observed that the mixed Cassie–Baxter/Wenzel state can be restored to the original Cassie–Baxter state by applying ultrasonic vibration which supplies energy to overcome the energy barrier for the wetting transition. In contrast, when the surface is fully wetted (classical Wenzel state), such restoration is not observed with ultrasonic vibration. The results reveal that although the superhydrophobic lotus leaves are susceptible to being wetted by condensing moisture, the configured wetting state is intermediate between the classical Cassie–Baxter and Wenzel states.     

Modification of wetting properties of laser-textured surfaces by depositing triboelectrically charged Teflon particles

Hydrophilic laser-textured silicon wafers with natural oxide surfaces were rendered hydrophobic by depositing electrostatically charged submicrometer Teflon particles, a process termed as triboelectric Teflon adhesion. Silicon surfaces were micro-textured (～5 μm) by laser ablation using a nanosecond pulsed UV laser. By varying laser fluence, micro-texture morphology of the wafers could be reproduced and well controlled. Wetting properties of the triboelectrically charged Teflon-deposited surfaces were studied by measuring apparent static water contact angles and water contact angle hysteresis as a function of substrate roughness and the amount of Teflon deposited. A similar study was also performed on various micro-textured silicon carbide surfaces (sandpapers). If the average substrate roughness is between 15 and 60 μm, superhydrophobic surfaces can be easily formed by Teflon deposition with water contact angle hysteresis less than 8°. This environmentally benign solvent-free process is a highly efficient, rapid, and inexpensive way to render contact-charged rough surfaces hydrophobic or superhydrophobic.     

表面微图案化聚乳酸膜的制备及其细胞亲和性评价

利用溶剂-非溶剂法(SNS)制备表面具有微孔图案的聚乳酸(PLA)膜和聚苯乙烯(PS)膜,并以微孔PS膜为模板,构建表面具有微岛图案的PLA膜.以此为基础,对所制备的微图案表面对PLA膜亲/疏水性及成骨细胞粘附与增殖性能的影响进行研究.结果显示微图案的存在显著增强了PLA膜的表面疏水性(水接触角90°);成骨细胞在微图案表面具有良好的铺展性,其黏附数量明显高于光滑PLA膜,但细胞的生长曲线相对较平缓,显示微图案表面虽有利于细胞在PLA膜表面的粘附与铺展,但对促进细胞的增殖无贡献.     

仿生沉积法制备水下低气体黏附透明材料

透明材料常用于水下设备中,而聚合物透明材料多较为疏水,在水下易黏附气泡,影响其光学性能.利用多巴胺(DA)和聚乙烯亚胺(PEI)共沉积技术,在多种透明聚合物材料表面构建了亲水/水下超疏气涂层.结果表明,聚多巴胺(PDA)与PEI可通过Michael加成或Schiff碱反应在此类材料表面形成亲水交联网络,显著提高其表面亲水性.表现为水接触角显著降低,而水下气接触角显著提高(140?),气泡在材料表面的黏附力显著下降.沉积时间在6 h以下时,XPS和椭圆偏振测试的结果表明,虽然所选用的透明材料表面沉积量和沉积厚度随时间有所上升,但其透光性不会受到显著影响.该方法具有较强的普适性,可用于多种水下气体黏附性较强的透明高分子材料,如聚苯乙烯(PS)、聚对苯二甲酸乙二醇酯(PET)、聚甲基丙烯酸甲酯(PMMA)、聚丙烯(PP)和聚酰亚胺(PI)等.同时,该方法形成的涂层的长期稳定性也较好,材料在水中浸泡振荡10天之后仍能保持较好的抗气泡黏附能力.该方法适用于如潜水艇舷窗、护目镜、水下光学镜头及其防护罩等水下设备中.     

New approach to fabricate an extremely super‐amphiphobic surface based on fluorinated silica nanoparticles

Superoleophobic surfaces possessing static contact angles greater than 140° with organic liquids are extremely rare. A simple approach has been developed to fabricate an extremely superamphiphobic coating material based on fluorinated silica nanoparticles resulting contact angles of water and diiodomethane at 167.5° and 158.6°, respectively. The contact angle of diiodomethane at 158.6° is substantially higher than the highest literature reported value we know of at 110°. In addition, this developed film also possesses extremely high contact angles with other organic liquids such as soybean oil (146.6°), decahysronaphthalene (142.5°), diesel fuel (140.4°), and xylene (140.5°). This developed superamphiphobic organic–inorganic hybrid film possesses unique liquid repellency for both water and organic liquids that can be used as functional coatings on numerous substrates by a simple coating process. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1984–1990, 2008     

Fabrication of robust superhydrophobic coatings using PTFE‐MWCNT nanocomposite: Supercritical fluid processing

Fabrication of polymer‐carbon composite nanostructure with good dispersion of each other is critical for the desired application due to the nanostructure flaws, agglomeration, and poor absorption between the 2 materials. Fabrication of superhydrophobic surface coating composites of polytetrafluoroethylene (PTFE) with multiwalled carbon nanotubes (MWCNTs) through supercritical fluid processing was explored in this study. Homogeneity of the composite was characterized by X‐ray diffraction and Raman spectroscopy studies, which reveal that the PTFE and MWCNT are uniform in the composite. Microstructural surface evaluation of field‐emission scanning electron microscope and high‐resolution transmission electron microscope studies display that the coating composite possesses roughness structures and fibrillation of the superhydrophobic surface coating. Superhydrophobic character was evaluated on fiber‐reinforced plastic (FRP) sheets, which showed that the prepared coating composite surface showed self‐cleaning properties with a high water contact angle of 162.7°. The surface wettability was studied by increasing different temperatures (30°C to 300°C) in PTFE‐MWCNT composite, which reveals that the FRP sheets were thermally stable up to 200°C and afterward; they transformed from superhydrophobic to hydrophilic state at 250°C. The superhydrophobic surfaces are thermally stable in extreme environmental conditions, and this technique may be used and extendable for large‐scale applications.     

Preparation and Characterisation of Super‐Hydrophobic Surfaces

The interest in highly water‐repellent surfaces has grown in recent years due to the desire for self‐cleaning surfaces. A super‐hydrophobic surface is one that achieves a water contact angle of 150° or greater. This article explores the different approaches used to construct super‐hydrophobic surfaces and identifies the key properties of each surface that contribute to its hydrophobicity. The models used to describe surface interaction with water are considered, with attention directed to the methods of contact angle analysis. A summary describing the different routes to hydrophobicity is also given.     

Evaluation of the Effect of Plasma Treatment Frequency on the Activation of Polymer Particles

This study investigates the influence of treatment frequency (1–150 kHz) on the atmospheric plasma activation of both silicone and polyethylene terephthalate (PET) particles. These polymer particles with diameters in the range 3–5 mm, were treated using either helium or helium/oxygen gas mixtures, in a barrel atmospheric plasma system. The level of polymer particles activation was monitored using water contact angle measurements. The effect of plasma treatment frequency on barrel heating was monitored using an infrared thermographic camera, the maximum barrel temperature after 15 min treatment was found to be 98 °C at a frequency of 130 kHz. Optical emission spectroscopy was used as a diagnostic tool to monitor changes in atomic and molecular species spectral intensity with experimental conditions, as well as a change in electron energy distribution function. Electrical characterisation studies demonstrated an increase in plasma power with increasing frequency, in the range investigated. X-ray photoelectron spectroscopy analysis indicate an increase of oxygen content on polymer surfaces after plasma treatment. For silicone particles, the minimum polymer water contact angle was obtained by using a frequency of 130 kHz. After 15 min treatment time, the water contact angle decreased from 141° to 11°. While for PET particles the optimum treatment frequency was found to be 70 kHz, resulting in a water contact angle decreased from 94° to 32°. This lower frequency was used due to the partial melting of the PET (Tg of 80 °C), when treated at the higher frequency.     

Bioinspired construction on aluminum alloy surfaces with stable super‐hydrophobicity and their resulting wettability

The bioinspired leaf‐like super‐hydrophobic surfaces on aluminum alloy were fabricated by means of a facile method using anodic oxidation. The surface morphologies, compositions, and wettability were investigated with SEM, XPS, and contact angle measurement, respectively. The SEM showed hierarchical microstructures and nanostructures, the static contact angle was about 167.7 ± 1.2°, and sliding angle was 5°. The super‐hydrophobic phenomenon of the prepared surface was analyzed with Cassie theory, and it is found that only about 3% of the water surface is contacted with the metal substrate and the remaining 97% is contacted with the air cushion. Copyright © 2011 John Wiley & Sons, Ltd.