Cleaning and hydrophilization of atomic force microscopy silicon probes

The silicon surface of commercial atomic force microscopy (AFM) probes loses its hydrophilicity by adsorption of airborne and package-released hydrophobic organic contaminants. Cleaning of the probes by acid piranha solution or discharge plasma removes the contaminants and renders very hydrophilic probe surfaces. Time-of-flight secondary-ion mass spectroscopy and X-ray photoelectron spectroscopy investigations showed that the native silicon oxide films on the AFM probe surfaces are completely covered by organic contaminants for the as-received AFM probes, while the cleaning methods effectively remove much of the hydrocarbons and silicon oils to reveal the underlying oxidized silicon of the probes. Cleaning procedures drastically affect the results of adhesive force measurements in water and air. Thus, cleaning of silicon surfaces of the AFM probe and sample cancelled the adhesive force in deionized water. The significant adhesive force values observed before cleaning can be attributed to formation of a bridge of hydrophobic material at the AFM tip-sample contact in water. On the other hand, cleaning of the AFM tip and sample surfaces results in a significant increase of the adhesive force in air. The presence of water soluble contaminants at the tip-sample contact lowers the capillary pressure in the water bridge formed by capillary condensation at the AFM tip-sample contact, and this consequently lowers the adhesive force.     

蝴蝶翅膀表面水滴各向异性黏附性质

采用扫描电子显微镜(SEM)观察了双带闪蝶(Morpho Achilles)翅膀表面的微观形貌, 通过样品的表观接触角表征了其浸润性, 采用高敏感性微电力学天平比较了水滴在蝴蝶翅膀表面不同方向运动时受到的黏附力. 实验结果表明, 水滴沿着干燥的蝴蝶翅膀鳞片堆叠方向运动时受到的黏附力要明显小于其它方向运动时受到的力, 且受力较稳定; 当蝴蝶翅膀被水滴浸润后, 水滴沿着湿润的蝴蝶翅膀鳞片堆叠方向运动时受到的黏附力接近甚至大于逆着鳞片堆叠方向运动时受到的力.     

Capillary forces between chemically different substrates

Motivated by experimental results, we present numerical and analytical calculations of the capillary force exerted by a capillary bridge spanning the gap between two parallel flat plates of asymmetric wettability. Depending on whether the sum of the two contact angles is smaller or larger than 180 degrees, the capillary force is either attractive or repulsive at small separations D between the plates. In either cases the magnitude of the force diverges as D approaches zero. The leading order of this divergence is captured by an analytical expression deduced from the geometry of the meniscus of a flat capillary bridge. The results for substrates with different wettability reveal an interesting behavior: with the sum of the contact angles fixed, the magnitude of the capillary force and the rupture separation decreases as the asymmetry in contact angles is increased. In addition, we present the rupture separation, i.e., the maximal extension of a capillary bridge, as a function of the contact angles. Our results provide an extensive picture of surface wettability effects on capillary adhesion.     

Effect of surface roughness and softness on water capillary adhesion in apolar media

The roughness and softness of interacting surfaces are both important parameters affecting the capillary condensation of water in apolar media, yet are poorly understood at present. We studied the water capillary adhesion between a cellulose surface and a silica colloidal probe in hexane by AFM force measurements. Nanomechanical measurements show that the Young's modulus of the cellulose layer in water is significantly less (~7 MPa) than in hexane (~7 GPa). In addition, the cellulose surface in both water and hexane is rather rough (6-10 nm) and the silica probe has a comparable roughness. The adhesion force between cellulose and silica in water-saturated hexane shows a time-dependent increase up to a waiting time of 200 s and is much (2 orders of magnitude) lower than that expected for a capillary bridge spanning the whole silica probe surface. This suggests the formation of one or more smaller bridges between asperities on both surfaces, which is confirmed by a theoretical analysis. The overall growth rate of the condensate cannot be explained from diffusion mediated capillary condensation alone; thin film flow due to the presence of a wetting layer of water at both the surfaces seems to be the dominant contribution. The logarithmic time dependence of the force can also be explained from the model of the formation of multiple capillary bridges with a distribution of activation times. Finally, the force-distance curves upon retraction show oscillations. Capillary condensation between an atomically smooth mica surface and the silica particle show less significant oscillations and the adhesion force is independent of waiting time. The oscillations in the force-distance curves between cellulose and silica may stem from multiple bridge formation between the asperities present on both surfaces. The softness of the cellulose surface can bring in additional complexities during retraction of the silica particle, also resulting in oscillations in the force-distance curves.     

Interfacial properties for real rough MEMS/NEMS surfaces by incorporating the electrostatic and Casimir effects–a theoretical study

This paper studied the adhesive properties of real rough micro/nano‐electromechanical systems (MEMS/NEMS) surfaces by considering the electrostatic force and the Casimir force theoretically, and an improved model has been proposed. A statistical approach for characterizing surface topography was used by taking the surface standard deviation, the asperity density and the radius of curvature into account. The effects of surface roughness on the electrostatic force and the Casimir force were analysed individually, and a comparison between the proposed model and existing models has been conducted. The whole adhesive force increases with the surface standard deviation, and the prediction by the proposed model becomes more in agreement with the one by existing models when the surface standard deviation is increased. The contribution of the Casimir force to the total adhesive force tends to vanish when the surface standard deviation is relatively large. The electrostatic force and the Casimir force contribute more to the total adhesive forces calculated based on the proposed model with the increase of the asperity density and the radius of curvature. Copyright © 2009 John Wiley & Sons, Ltd.     

Controlling the formation of capillary bridges in binary liquid mixtures

We study the formation of capillary bridges between micrometer-sized glass spheres immersed in a binary liquid mixture using bright field and confocal microscopy. The bridges form upon heating due to the preferential wetting of the hydrophilic glass surface by the water-rich phase. If the system is cooled below the demixing temperature, the bridges disappear within a few seconds by intermolecular diffusion. Thus, this system offers the opportunity to switch the bridges on and off and to tune precisely the bridge volume by altering the temperature in a convenient range. We measure the bridge geometry as a function of the temperature from bright field images and calculate the cohesive force. We discuss the influence of the solvent composition on the bridge formation temperature, the strength of the capillary force, and the bridge volume growth rate. Furthermore, we find that the onset of bridge formation coincides with the water-lutidine bulk coexistence curve.     

Experimental humidity dependency of small particle adhesion on silica and titania

The humidity present in ambient atmosphere affects the adhesion of small particles by causing capillary bridge formation between the particle and the surface. Even in moderate relative humidities this, usually attractive, force can have a significant effect on adhesion behaviour of micro and sub-micro particles. We have directly measured the pull-off forces of initially adhered oxide particles on oxide surfaces with atomic force microscope in controlled atmosphere with adjustable humidity. We demonstrate the effect of the surface roughness resulting in two different regions of capillary formation and the particle shape having a strong effect on the humidity dependency of adhesion. The experimental results are explained by theoretical framework.     

Nanoscale characterization of different stiction mechanisms in electrostatically driven MEMS devices based on adhesion and friction measurements

In this work, for the first time different stiction mechanisms in electrostatic micro-electromechanical systems (MEMS) switches were studied. In these devices stiction can be caused by two main mechanisms: dielectric charging and meniscus formation resulting from the adsorbed water film between the switch bridge and the dielectric layer. The effect of each mechanism and their interaction were investigated by measuring the adhesive and friction forces under different electrical stress conditions and relative humidity levels. An atomic force microscope (AFM) was used to perform force-distance and friction measurements on the nanoscale. A novel technique was proposed to measure the induced surface potential over the dielectric surface and was used to explain the obtained adhesive and friction results. The evolution of adhesive force with time was monitored in order to study the charging/discharging processes in the dielectric film. The assessment methodology is employed for application in RF-MEMS switches and could be extended to other electrostatic MEMS devices. The study provides an in-depth understanding of different stiction mechanisms, and explanation for the literature reported device level measurements for electrostatic capacitive MEMS switches.     

Spectral force analysis using atomic force microscopy reveals the importance of surface heterogeneity in bacterial and colloid adhesion to engineered surfaces

Coatings developed to reduce biofouling of engineered surfaces do not always perform as expected based on their native properties. One reason is that a relatively small number of highly adhesive sites, or the heterogeneity of the coated surface, may control the overall response of the system to initial bacterial deposition. It is shown here using an approach we call spectral force analysis (SFA), based on force volume imaging of the surface with atomic force microscopy, that the behavior of surfaces and coatings can be better understood relative to bacterial adhesion. The application of vapor deposited TiO₂ metal oxide increased bacterial and colloid adhesion, but coating the surface with silica oxide reduced adhesion in a manner consistent with SFA based on analysis of the “stickiest” sites. Application of a TiO₂-based paint to a surface produced a relatively non-fouling surface. Addition of a hydrophilic layer coating to this surface should have decreased fouling. However, it was observed that this coating actually increased fouling. Using SFA it was shown that the reason for the increased adhesion of bacteria and particles to the hydrophilic layer was that the surface produced by this coating was highly heterogeneous, resulting in a small number of sites that created a stickier surface. These results show that while it is important to manufacture surfaces with coatings that are relatively non-adhesive to bacteria, it is also essential that these coatings have a highly uniform surface chemistry.     

Mechanical properties and biodegradability of poly-?-caprolactone/soy protein isolate blends compatibilized by coconut oil

This study was performed for the mechanical properties, adhesion properties and biodegradability depending on the coconut oil content based on poly-?-caprolactone (PCL):soy protein isolate (SPI) blends. Coconut oil was capable of forming the PCL:SPI blend. Tensile strength (TS) of the blend decreased and elongation at break (EAB) increased when the concentration of coconut oil increased. Lap shear strength of all samples was observed in the values of the general formulated hot-melt but in particularly, high adhesive strength was shown at 20 mL of coconut oil. The improvement of surface hydrophilicity and biodegradation resulted from the addition of SPI rather than coconut oil. Consequently, coconut oil acted as a plasticizer and compatibilizer although it did not enhance in biodegradation and surface hydrophilicity.     

Rupture energy and wetting behavior of pendular liquid bridges in relation to the spherical agglomeration process

A novel micro force balance (MFB) is used to investigate the rupture energy of a silicon oil liquid bridge formed in water between two glass particles of either the same or dissimilar surface energy. Rupture energies are integrated from force curves and compared with the models proposed by Simons et al. (Chem. Eng. Sci. 49 (1994) 2331) and Pitois et al. (Eur. Phys. J. B 23 (2001) 79). The latter showed slightly better agreement to the experimental data. Glass ballotini ( approximately 100 microm diameter) are either silanized, in order to increase their wettability toward the oil binder, or kept untreated. Results showed how the interaction between the binder and the particle influences the geometry, the capillary pressure, the force, and the rupture energy of the liquid bridge. Higher values of force and liquid bridge energy were measured between particles characterized by higher interaction (silanized-silanized configuration). A thermodynamic approach to the evaluation of the energy stored in a liquid bridge is also proposed. The mechanical work done to stretch apart the liquid bridge is evaluated as the difference of internal and hysteresis energy between the initial and the rupture configuration of the bridge. This approach showed good agreement with the experimental data only for liquid bridges formed between silanized and untreated glass particles.     

Formation of functional nanofibrous electrospun polyurethane and murivenna oil with improved haemocompatibility for wound healing

Electrospinning is an emerging tool and promising method to fabricate polymer nanofibers. The aim of this work was to fabricate electrospun polyurethane mats reinforced with murivenna oil for wound dressings. The scanning electron microscopy (SEM) micrographs showed the fiber diameter of nanocomposites in the range of 740 ± 160 nm and found to be decreased compared to pure polyurethane. Surface of nanocomposites was analyzed by Fourier transform infrared spectroscopy (FTIR) insinuated the interactions between PU and murivenna oil by the formation of hydrogen bond and changes in the characteristics peaks. Contact angle of the PU incorporated murivenna oil showed a decrease in its value compared to pure PU indicating the increased wettability and hydrophilic nature. The thermal degradation and stability of fabricated composites was found be enhanced compared to pure PU. The surface morphology through atomic force microscopy (AFM) analysis showed a change in surface roughness due to presence of murivenna oil in the polymer matrix. In blood compatibility results, both activated partial thromboplastin time (APTT) and prothrombin time (PT) were delayed due to improved surface properties and the addition of murivenna oil in the PU matrix. Compared to pure PU, the hemolysis assay of the PU incorporated murivenna oil showed a significant decrease in the percentage of lysis of red blood cells indicating better blood compatibility. Following the results, it was confirmed that fabricated novel scaffolds having better physicochemical and enhanced blood compatibility properties may be utilized for wound dressing.     

A new approach to describe the skin surface physical properties in vivo

In the present paper, we describe a new mechanical method characterising the physico-chemical properties of human skin and their variations along with liquid exposure scenario to the skin surface. A specific bio-tribometer has been developed to study the physical properties of the skin in vivo by measuring the maximum adhesion force between the skin and the bio-tribometer. We showed that the lipidic film present on skin surface was responsible for skin adhesion due to capillary phenomena. The measure of pull-off force between skin and bio-tribometer has permitted to estimate the liquid/vapour surface tension of the lipidic film (γ_LV ≈ 6.3 mJ/m² in 30-year-old volunteer). The kinetic of sorption/desorption (sorption means indifferently adsorption and absorption process) of distilled water from the skin has been observed through the variation of the indenter/skin pull-off force versus time after distilled water application to the skin surface. This permits to follow in real time the variation of the skin physico-chemical properties after liquid application onto the skin surface. Finally, the increasing of skin friction coefficient after distilled water application onto skin surface was explained by the capillary adhesion force between the probe and the skin.     

Capillary forces between two spheres with a fixed volume liquid bridge: theory and experiment

Capillary forces are commonly encountered in nature because of the spontaneous condensation of liquid from surrounding vapor, leading to the formation of a liquid bridge. In most cases, the advent of capillary forces by condensation leads to undesirable events such as an increase in the strength of granules, which leads to flow problems and/or caking of powder samples. The prediction and control of the magnitude of capillary forces is necessary for eliminating or minimizing these undesirable events. The capillary force as a function of the separation distance, for a liquid bridge with a fixed volume in a sphere/plate geometry, was calculated using different expressions reported previously. These relationships were developed earlier, either on the basis of the total energy of two solid surfaces interacting through the liquid and the ambient vapor or by direct calculation of the force as a result of the differential gas pressure across the liquid bridge. It is shown that the results obtained using these methodologies (total energy or differential pressure) agree, confirming that a total-energy-based approach is applicable, despite the thermodynamic nonequilibrium conditions of a fixed volume bridge rupture process. On the basis of the formulas for the capillary force between a sphere and a plane surface, equations for the calculation of the capillary force between two spheres are derived in this study. Experimental measurements using an atomic force microscope (AFM) validate the formulas developed. The most common approach for transforming interaction force or energy from that of sphere/plate geometry to that of sphere/sphere geometry is the Derjaguin approximation. However, a comparison of the theoretical formulas derived in this study for the interaction of two spheres with those for sphere/plate geometry shows that the Derjaguin approximation is only valid at zero separation distance. This study attempts to explain the inapplicability of the Derjaguin approximation at larger separation distances. In particular, the area of a liquid bridge changes with the separation distance, H, and thereby does not permit the application of the "integral method," as used in the Derjaguin approximation.     

气相色谱-质谱测定樟林番荔枝种子挥发油的脂肪酸组成

用溶剂萃取法提取樟林番荔枝果实种子中的挥发性物质,测定出其挥发油质量分数为13.3%;利用GC-MS方法分离确认出其中的9种化学成分;用面积归一化法得出了9种脂肪酸在挥发油中的质量分数;其中9-十八烯酸占49.42%,十六酸占20.37%,十八酸占14.16%,9,2-十八二烯酸占13.59%;不饱和脂肪酸,占63.01%.该项研究给番荔枝果实的深入开发利用及种质资源的有效保护提供了科学依据.     

Non-DLVO silica interaction forces in NMP-water mixtures. II. An asymmetric system

The interaction between energetically asymmetric hydrophilic and hydrophobic surfaces has fundamental and practical importance in both industrial and natural colloidal systems. The interaction forces between a hydrophilic silica sphere and a silanated, hydrophobic glass plate in N-methyl-2-pyrrolidone (NMP)-water binary mixtures were measured using atomic force microscopy (AFM). A strong and long-range attractive force was observed in pure water and was attributed to the formation of capillary bridges associated with nanoscale bubbles initially present on the hydrophobic surface. When NMP was added, the capillary force and corresponding pull-off force became less attractive, which was explained readily in terms of the surface wettability by the binary solvent mixture. Similar to the case of symmetric (two hydrophilic) surfaces, the range of attraction between the asymmetric surfaces was maximized at around 30 vol % NMP, which is consistent with the formation of a thick adsorbed macrocluster layer on the hydrophilic silica surface.     

Particle-surface capillary forces with disjoining pressure

A new, atomic force microscopy (AFM) based experimental setup for the continuous acquisition of friction force data as a function of humidity has been developed. The current model of interactions between wet contacts under the influence of capillary effects, has been amended to include a vertical component due to the disjoining pressure and takes into account the influence of liquid films adsorbed on the surface. This is a 'switching' model, i.e. the contact between nanometer-sized sphere and a flat surface can exist in two distinct states due to capillary bridge formation/destruction as the humidity is varied. The model has been qualitatively verified on samples of differing wettability produced by UV-ozone treatment of polystyrene (PS). Results of AFM analysis of the friction vs. vapor pressure curves collected from the surface are presented. Correlation between important surface properties such as wettability, adsorption, and contact angle and friction force under varying humidity were found and discussed.     

A Surfactant Bridge Model for the Nonlinear Electrorheological Effects of Surfactant-Activated ER Suspensions

In surfactant-activated electrorheological (ER) suspensions it is observed that the ER response shows linear ER behavior (F~E(2)) at small surfactant concentrations and nonlinear ER behavior (F~E(n), n approximately 1) at large surfactant concentrations. Here, a surfactant bridge model is developed to explain the nonlinear ER behavior of surfactant-activated ER suspensions. The model shows that the formation and size of a surfactant bridge depend on various variables, especially the electric field strength, the surfactant surface tension, and the initially adsorbed amount of surfactants on particles. The predicted dependence of the formation and size of a surfactant bridge on the electric field strength and the initially adsorbed amount of surfactants is consistent with the observations. Also, the model indicates that there is a critical minimum electric field E(crit) for the formation of a surfactant bridge, and the estimated E(crit) shows good agreement with the observations. The force acting between particles is composed of the electrostatic force and force associated with surface tension. However, it is found that the contribution of the force associated with surface tension can be ignored and the electrostatic force is dominant regardless of the formation of surfactant bridges between particles. When surfactant bridges are formed between particles, the predicted force shows nonlinear ER behavior (F~E(n), n approximately 1), consistent with the observed nonlinear ER behavior at large surfactant concentrations. When no surfactant bridge is formed, the predicted force is proportional to the electric field squared (F~E(2)), consistent with the interfacial polarization. The model can successfully predict the nonlinear ER behavior at large surfactant concentrations, confirming that the nonlinear ER behavior of surfactant-activated ER suspensions arises from the observed formation of surfactant bridges between particles. Copyright 2001 Academic Press.     

人造玫瑰花花瓣的微结构分布与水滴黏附性质的关系

本文采用模板印刷法制备得到了“人造玫瑰花花瓣”,即具有玫瑰花花瓣结构的PDMS薄膜,通过对该薄膜逐级拉伸改变微观结构的分布;采用环境扫描电镜（ESEM）观察了不同拉伸程度下薄膜表面微观结构的变化,采用高敏感性微电力学天平测试了样品表面微观结构变化过程中水滴的粘附力,分析了微观结构分布与水滴粘附性质的关系;采用接触角测量仪表征不同拉伸条件下薄膜的浸润性.实验结果表明随着PDMS薄膜被逐次拉伸,单位面积内玫瑰花花瓣乳突的数目减少,纳米褶皱面积不断增加,而纳米级褶皱结构尺寸随着拉伸基本上不发生变化,直到样品破坏;与微观结构变化相对应的,该表面对水滴的粘附力先增大后减小,直到该表面彻底破坏.由此可见,微米结构及纳米结构的分布是影响玫瑰花花瓣对水滴粘附的主要因素.     

Effects of adsorbed water layer structure on adhesion force of silicon oxide nanoasperity contact in humid ambient

The origin of the large relative-humidity (RH) dependence of the adhesion force in the single-asperity contact between silicon oxide surfaces is elucidated. As RH increases, the adhesion force measured with an atomic force microscopy (AFM) initially increases, reaches a maximum, and then decreases at high RH. The capillary force alone cannot explain the observed magnitude of the RH dependence. The origin of the large RH dependence is due to the presence of an icelike structured water adsorbed at the silicon oxide surface at room temperature. A solid-adsorbate-solid model is developed calculating the contributions from capillary forces, van der Waals interactions, and the rupture of an ice-ice bridge at the center of the contact region. This model illustrates how the structure, thickness, and viscoelastic behavior of the adsorbed water layer influence the adhesion force of the silicon oxide nanoasperity contact.