Direct Measurement Of Surface Forces Research Articles

Ternary Synergy of Lys, Dopa, and Phe Results in Strong Cohesion of Peptide Films.

Synergistic interactions between 3,4-dihydroxyphenylalanine (Dopa, Y*), cationic residues, and the aromatic rings have been recently highlighted as influential factors that enhance the underwater adhesion strength of mussel foot proteins and their derivatives. In this study, we report the first ever evidence of a cation-catechol-benzene ternary synergy between Y*, lysine (Lys, K), and phenylalanine (Phe, F) in adhesive peptides. We synthesized three hexapeptides containing a different combination of Y*, K, and F, i.e., (KY*)3, (KF)3, and (KY*F)2, respectively, exploring the relationship between the cohesive performance and molecular architecture of peptides. The peptide with the (KY*F)2 sequence displays the strongest underwater cohesion energy of 10.3 ± 0.3 mJ m-2 from direct nanoscale surface force measurements. Combined with molecular dynamics simulation, we demonstrated that there are more bonding interactions (including cation-π, π-π, and hydrogen bond interactions) in (KY*F)2 compared to the other two peptides. In addition, peptide (KY*F)2 still shows the strongest cohesive energies of 7.6 ± 0.7 and 3.7 ± 0.5 mJ m-2 in acidic and high-ionic strength environments, respectively, although the cohesive energy decreases compared to the value in pure water. Our results further explain the underwater cohesion mechanisms combining multiple interactions and offer insights on designing Dopa containing underwater adhesives.

Bench-scale oil fouling/antifouling tests under high temperature and high pressure conditions and the underlying interfacial interaction mechanisms

Oil fouling is commonly encountered in many environmental and engineering fields and remains a challenging issue. The fouling issue in steam-assisted gravity drainage (SAGD) process for extracting bitumen from oil sands deposits has received much attention from oil industry. In view of low capital investment and exceptional antifouling performance, adding antifoulants has emerged as a promising strategy for addressing fouling issues. Developing an efficient method to evaluate their antifouling performance under production conditions is urgently needed. In this work, we report a novel bench-scale test method for quantitatively evaluating the antifouling performance of antifoulants under high temperature and high pressure (HTHP), close to SAGD operation conditions. The effects of antifoulant dosage and stirring rate on the antifouling performance are systematically investigated. The underlying fouling and antifouling mechanisms are characterized through direct molecular and surface force measurements. It is found that the commercial antifoulant exhibits exceptional antifouling performance at the dosage range of 20–35 ppm, and increasing stirring rate enhances the antifouling behavior. The force measurement results indicate that the antifoulant can adsorb to organics and target substrate surfaces, performing the antifouling function by lowering the hydrophobic interaction between organics and target substrates. This work provides a novel and feasible method for characterizing fouling phenomena and evaluating antifoulants under HTHP conditions and improves the understanding of fundamental interaction mechanisms underlying the fouling and antifouling phenomena.

Probing Hydrophobic Interactions between Polymer Surfaces and Air Bubbles or Oil Droplets: Effects of Molecular Weight and Surfactants.

Hydrophobic interaction plays an important role in numerous interfacial phenomena and biophysical and industrial processes. In this work, polystyrene (PS) was used as a model hydrophobic polymer for investigating its hydrophobic interaction with highly deformable objects (i.e., air bubbles and oil droplets) in aqueous solutions. The effects of polymer molecular weight, solvent (i.e., addition of ethanol to water), the presence of surface-active species, and hydrodynamic conditions were investigated, via direct surface force measurements using the bubble/drop probe atomic force microscopy (AFM) technique and theoretical calculations based on the Reynolds lubrication theory and augmented Young-Laplace equation by including the effect of disjoining pressure. It was found that the PS of low molecular weight (i.e., PS590 and PS810) showed slightly weaker hydrophobic interactions with air bubbles or oil droplets, as compared to glassy PS of higher molecular weight (i.e., PS1110, PS2330, PS46300, and PS1M). The hydrophobic interaction between PS and air bubbles in a 1 M NaCl aqueous solution with 10 vol % ethanol was weaker than that in the bare aqueous solution. Such effects on the hydrophobic interactions are possibly achieved by influencing the structuring/ordering of water molecules close to the hydrophobic polymer surfaces by tuning the surface chain mobility and surface roughness of polymers. It was found that the addition of three surface-active species, i.e., cetyltrimethylammonium chloride (CTAC), Pluronic F-127, and sodium dodecyl sulfate (SDS), to the aqueous media could suppress the attachment of the hydrophobic polymer and air bubbles or oil droplets, most likely caused by the additional steric repulsion due to the adsorbed surface-active species at the bubble/polymer/oil interfaces. Our results have improved the fundamental understanding of the interaction mechanisms between hydrophobic polymers and gas bubbles or oil droplets, with useful implications on developing effective methods for modulating the related interfacial interactions in many engineering applications.

Direct measurement of surface forces: Recent advances and insights

The direct measurement of forces between atomically smooth mica surfaces down to sub-nanometer separation was pioneered over 50 years ago and has yielded deep understanding of a range of interfacial effects, not least the forces that determine colloidal stability and self-assembly, the properties of highly confined fluids, and the molecular origin of friction and lubrication. Here, we describe recent advances, including the use of substrates other than mica, probing the shear properties of highly confined fluids including hydration layers, and the modulation of surface forces by surface-attached macromolecules and amphiphiles, together with microscopic imaging of the surface morphology. These advances enabled novel features such as external potential control of the interacting surfaces, new understanding of lubrication in aqueous and biological systems, the design of novel nanoparticles and surface assemblies for modulating frictional dissipation, and insight into the nature of long-ranged attraction between surfactant-hydrophobized surfaces. We conclude by briefly outlining future challenges and opportunities provided by such direct surface forces studies.

Phytoglycogen Nanoparticles: Nature-Derived Superlubricants.

Phytoglycogen nanoparticles (PhG NPs), a single-molecule highly branched polysaccharide, exhibit excellent water retention, due to the abundance of close-packed hydroxyl groups forming hydrogen bonds with water. Here we report lubrication properties of close-packed adsorbed monolayers of PhG NPs acting as boundary lubricants. Using direct surface force measurements, we show that the hydrated nature of the NP layer results in its striking lubrication performance, with two distinct confinement-controlled friction coefficients. In the weak- to moderate-confinement regime, when the NP layer is compressed down to 8% of its original thickness under a normal pressure of up to 2.4 MPa, the NPs lubricate the surface with a friction coefficient of 10-3. In the strong-confinement regime, with 6.5% of the original layer thickness under a normal pressure of up to 8.1 MPa, the friction coefficient was 10-2. Analysis of the water content and energy dissipation in the confined NP film reveals that the lubrication is governed by synergistic contributions of unbound and bound water molecules, with the former contributing to lubrication properties in the weak- to moderate-confinement regime and the latter being responsible for the lubrication in the strong-confinement regime. These results unravel mechanistic insights that are essential for the design of lubricating systems based on strongly hydrated NPs.

Surface Forces and Structure in a Water-in-Salt Electrolyte.

Water-in-salt electrolytes are a fascinating new class of highly concentrated aqueous solutions with wide electrochemical stability windows that make them viable as aqueous battery electrolytes. However, the high ion concentration of water-in-salt electrolytes means that these systems are poorly understood when compared to more dilute electrolyte solutions. Here, we present direct surface force measurements across thin films of a water-in-salt electrolyte at several concentrations. We find that the electrolyte adopts a layered structure at charged interfaces composed of a nanostructure of a hydrated cation and nonaqueous anion-rich domains. These observations will aid in the interpretation of capacitance and double-layer behavior of water-in-salt electrolytes with consequences for their use in energy storage devices.

A 3-mirror surface force balance for the investigation of fluids confined to nanoscale films between two ultra-smooth polarizable electrodes.

We present a new technique, based on the Surface Force Balance (SFB), for the direct measurement of surface forces between two ultra-smooth and polarizable gold electrode surfaces across thin fluid films. Combining the direct interferometric measurement of surface separation and contact geometry with smooth electrode surfaces has proved challenging in the past, and for this reason, previous measurements with the SFB typically involved two insulating mica surfaces, or one mica surface and one electrode surface, or an alternative less direct measure of the surface separation. Here, we demonstrate that a 3-mirror interferometer can overcome these difficulties: the setup involves two ultra-smooth electrode/mirror surfaces between which the fluid is confined and a third mirror to allow for interferometric detection of the liquid thickness with nanometer resolution and at thicknesses much smaller than the diffraction limit of the light. We conclude with a proof-of-concept measurement across dry nitrogen gas. The technique should prove useful for studying the properties of fluids confined at the nanoscale inside a slit-pore of controlled electrical potential or subject to applied electric fields.

An identification of the soft polyelectrolyte gel-like layer on silica colloids using atomic force and electron microscopy

A procedure is introduced for measuring the radius of spherical colloid particles from the curvature of upper parts of their central cross-sectional profiles obtained by atomic force microscopy (AFM). To minimize the possible compression and displacement of the spheres, AFM is operated in a mode rendering a constant ultralow pN force on the tip. The procedure allows us to evaluate the mean radius of nearly monodisperse submicrometer spheres of silica in their natively hydrated state in aqueous electrolyte solutions, irrespective of whether they are coagulated or not. A variation in the volume (swelling degree) of layers delimited by the AFM mean radii of these spheres in KCl solutions and their invariable mean radius in vacuum is obtained that follows a scaling power law derived in polymer physics for swellable polyelectrolyte gels and deduced previously by us from coagulation tests. This supports our former suggestion about the existence of soft polyelectrolyte gel-like layer developed spontaneously around silica surfaces and colloids. We discuss this finding in the context of recent knowledge about the structure of the silica/water interface obtained from direct surface force measurements between macroscopic silica surfaces and from particle size measurements of silica colloids and highlight its importance for colloid chemistry and condensed mattter physics.

表面間力の直接測定：

多くの工業分野で重要である液体中の微粒子分散系を扱ううえでは，その分散・凝集を適切に評価し，制御することが必要である。分散系の粒子の分散・凝集は粒子間に働く相互作用力（表面間力）によってほぼ支配されているため，粒子表面の性質や構造，あるいは溶媒の種類，条件などによる表面間力を正確に見積もることが，分散・凝集の適切な評価には重要である。本稿では，この表面間力の直接測定方法およびその研究動向と，そこから得られた知見について述べる。とくに，溶媒・溶質分子の表面吸着や構造の形成などといった，ナノスコピックな界面の構造・性質が表面間力を本質的にいかに変化させるかを俯瞰する。

Modifying surface forces through control of surface potentials.

Combining direct surface force measurements with in situ regulation of surface potential provides an exceptional opportunity for investigating and manipulating interfacial phenomena. Recently, we studied the interaction between gold and mica surfaces in water with no added salt, while controlling the metal potential, and found that the surface charge at the metal may vary, and possibly even change its sign, as it progressively approaches the (constant-charge) mica surface [Langmuir, 2015, 31(47), 12845-12849]. Such a variation was found to directly affect the nature of the contact and adhesion between them due to exclusion of all mobile counterions from the intersurface gap. In this work, we extend this to examine the potential-dependent response of the adhesion and interaction between gold and mica to externally applied voltages and in electrolyte solution. Using a surface force balance (SFB) combined with a three-electrode electrochemical cell, we measured the normal interaction between gold and mica under surface potential regulation, revealing three interaction regimes - pure attraction, non-monotonic interaction from electrostatic repulsion to attraction (owing to charge inversion) and pure repulsion. Accordingly, the adhesion energy between the surfaces was found to vary both in no added salt water and, more strongly, in electrolyte solution. We justify this potential-dependent variation of adhesion energy in terms of the interplay between electrostatic energy and van der Waals (vdW) interaction at contact, and attribute the difference between the two cases to the weaker vdW interaction in electrolyte solution. Finally, we showed that through abruptly altering the gold surface potential from negative to positive and vice versa, the adhesion between gold and mica can be reversibly switched on and off. We surmise that the process of bringing the surface into contact is associated with the formation of a strong electric field O (108 V m-1) in the intersurface gap.

Probing Anisotropic Surface Properties of Molybdenite by Direct Force Measurements.

Probing anisotropic surface properties of layer-type mineral is fundamentally important in understanding its surface charge and wettability for a variety of applications. In this study, the surface properties of the face and the edge surfaces of natural molybdenite (MoS2) were investigated by direct surface force measurements using atomic force microscope (AFM). The interaction forces between the AFM tip (Si3N4) and face or edge surface of molybdenite were measured in 10 mM NaCl solutions at various pHs. The force profiles were well-fitted with classical DLVO (Derjaguin-Landau-Verwey-Overbeek) theory to determine the surface potentials of the face and the edge surfaces of molybdenite. The surface potentials of both the face and edge surfaces become more negative with increasing pH. At neutral and alkaline conditions, the edge surface exhibits more negative surface potential than the face surface, which is possibly due to molybdate and hydromolybdate ions on the edge surface. The point of zero charge (PZC) of the edge surface was determined around pH 3 while PZC of the face surface was not observed in the range of pH 3-11. The interaction forces between octadecyltrichlorosilane-treated AFM tip (OTS-tip) and face or edge surface of molybdenite were also measured at various pHs to study the wettability of molybdenite surfaces. An attractive force between the OTS-tip and the face surface was detected. The force profiles were well-fitted by considering DLVO forces and additional hydrophobic force. Our results suggest the hydrophobic feature of the face surface of molybdenite. In contrast, no attractive force between the OTS-tip and the edge surface was detected. This is the first study in directly measuring surface charge and wettability of the pristine face and edge surfaces of molybdenite through surface force measurements.

Ionic liquids behave as dilute electrolyte solutions

We combine direct surface force measurements with thermodynamic arguments to demonstrate that pure ionic liquids are expected to behave as dilute weak electrolyte solutions, with typical effective dissociated ion concentrations of less than 0.1% at room temperature. We performed equilibrium force-distance measurements across the common ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]) using a surface forces apparatus with in situ electrochemical control and quantitatively modeled these measurements using the van der Waals and electrostatic double-layer forces of the Derjaguin-Landau-Verwey-Overbeek theory with an additive repulsive steric (entropic) ion-surface binding force. Our results indicate that ionic liquids screen charged surfaces through the formation of both bound (Stern) and diffuse electric double layers, where the diffuse double layer is comprised of effectively dissociated ionic liquid ions. Additionally, we used the energetics of thermally dissociating ions in a dielectric medium to quantitatively predict the equilibrium for the effective dissociation reaction of [C4mim][NTf2] ions, in excellent agreement with the measured Debye length. Our results clearly demonstrate that, outside of the bound double layer, most of the ions in [C4mim][NTf2] are not effectively dissociated and thus do not contribute to electrostatic screening. We also provide a general, molecular-scale framework for designing ionic liquids with significantly increased dissociated charge densities via judiciously balancing ion pair interactions with bulk dielectric properties. Our results clear up several inconsistencies that have hampered scientific progress in this important area and guide the rational design of unique, high-free-ion density ionic liquids and ionic liquid blends.

Paradox of Stability of Nanoparticles at Very Low Ionic Strength

The scaling of electrical double layer interaction energy from a plate-plate system to a sphere-plate system was reexamined, and it was found that accurate scaling without resorting to the Derjaguin approximation theoretically predicts the destabilization of nanoparticles in water depleted of added electrolyte and, consequentially, a maximum stability at a moderate ionic strength. This theoretical feature re-emphasizes the dual-role nature of added electrolyte that was supported by experimental results of direct surface force measurement but not by those of colloidal stability of nanoparticle deposition/aggregation. Inconsistences between the theoretical prediction and the experimental observation and between experimental observations in different systems were discussed. Possible reasons leading to the inconsistences were explored, including the effect of curvature, the contribution from counterions, the mode of interaction, and the applicability of an equilibrium model to describe the colloidal interaction of a nanoparticle suspension.

EGR Cooler에 CNC 첨가시 열교환 특성에 관한 연구

Although combustion is essential in most energy generation processes, it is one of the major causes of air pollution. Circle fin exhaust pipes were designed to study the effect of cooling the recirculated exhaust gases (EGR) of Diesel engines on the chemical composition of the exhaust gases and the reduction in the percentages of pollutant emissions. The designs adopted in this study were exhaust pipes with solid and hollow fins around them direct surface force measurement in water using a nano size colloidal probe Technique The direct force measurement between colloidal surfaces has been an essential topic in both theories and applications of surface chemistry. As particle size is decreased from micron size down to true Carbon nano Colloid size (

The transmission interferometric adsorption sensor

This paper describes a high-speed adsorption sensor based on thin-film interference at the interfaces. The sensor can be used as a stand-alone instrument or in combination with a direct surface force measurement, which yields a wide range of additional information on molecular interactions on adsorbed films. The achieved mass resolution of the presented method (1–10 ng cm−2 Hz−1/2) is comparable to or better than other modern bio-sensors. The dependence of mass resolution on various factors is presented and demonstrated in a number of relevant examples. The described method is suitable for the implementation of a low-cost bio-sensor with a minimal number of optical elements.The measurement spot size is one micrometre or more and sampling rates >10 Hz are readily possible. In contrast to other bio-sensors, the signal baseline has a remarkable long-term stability since the measured signal is virtually independent of refractive index changes in the fluid medium above the sensor surface.In combination with an optical spectral correlation method, the classical computer calculations are substituted by an optical calculator and a label-free real-time imaging adsorption sensor is realized. We demonstrate sensor operation both inside the extended surface forces apparatus as well as in a stand-alone bio-sensor configuration. As a final point, we illustrate the imaging capability of this new sensor technology on a patterned bio-functionalized surface.

フロンティア研究シリーズ 液相中での表面間力の直接測定―疎水性引力を中心に―

Direct measurement of the interaction forces between solid surfaces in liquids has become an important technique in recent years for understanding the various microscopic phenomena that affect the behavior of fine particles in many industrial processes. The history and the development of the direct measurements of surface forces are briefly reviewed. As a practical example of the force measurements, a series of the investigations for hydrophobic attraction, which is the interaction between hydrophobic surfaces in aqueous solution, using an atomic force microscope is introduced.

Atomic force microscopy and direct surface force measurements (IUPAC Technical Report)

Abstract The atomic force microscope (AFM) is designed to provide high-resolution (in the ideal case, atomic) topographical analysis, applicable to both conducting and nonconducting surfaces. The basic imaging principle is very simple: a sample attached to a piezoelectric positioner is rastered beneath a sharp tip attached to a sensitive cantilever spring. Undulations in the surface lead to deflection of the spring, which is monitored optically. Usually, a feedback loop is employed, which holds the spring deflection constant, and the corresponding movement of the piezoelectric positioner thus generates the image. From this it can be seen that the scanning AFM has all the attributes necessary for the determination of surface and adhesion forces; a sensitive spring to determine the force, a piezoelectric crystal to alter the separation of the tip and surface, which if sufficiently well-calibrated also allows the relative separation of the tip and surface to be calculated. One can routinely quantify both the net surface force (and its separation dependence) as the probe approaches the sample, and any adhesion (pull-off) force on retraction. Interactions in relevant or practical systems may be studied, and, in such cases, a distinct advantage of the AFM technique is that a particle of interest can be attached to the end of the cantilever and the interaction with a sample of choice can be studied, a method often referred to as colloid probe microscopy. The AFM, or, more correctly, the scanning probe microscope, can thus be used to measure surface and frictional forces, the two foci of this article. There have been a wealth of force and friction measurements performed between an AFM tip and a surface, and many of the calibration and analysis issues are identical to those necessary for colloid probe work. We emphasize that this article confines itself primarily to elements of colloid probe measurement using the AFM.

Segregation in granular materials and the direct measurement of surface forces using atomic force microscopy

It is known that one of the dominant forces controlling the macroscopic motion of particles is the cohesive force due to the presence of liquid bridges between particles. In a mixing process, this force directly impacts the degree of homogeneity achievable by the system. The work presented here provides a quantitative analysis of this relationship through concurrent direct measurements of surface forces due to moisture and blending/segregation experiments. Atomic force microscopy (AFM) was employed to measure the force required to remove the AFM's cantilever from the surface of a glass bead with varying degrees of surface moisture. Corresponding blending/segregation experiments were performed using the same materials and conditions to develop a correlation between the interparticle forces due to the liquid layer and the final state of a mixing process. The extent to which greater moisture content increased the interparticle surface forces was quantified, and it was observed that segregation decreases proportionately to increases in surface forces.

Mechanism of Particle Deposition on Silicon Surface during Dilute HF Cleans

The mechanism of particle deposition onto silicon wafer surfaces during dilute HF cleans is discussed. Direct surface force measurement using an atomic force microscope showed that particle redeposition on a silicon surface is due to the dominant van der Waals interaction between the particle and the wafer surface. The addition of surfactants can affect the clean effectiveness of a dilute HF solution by changing the surface interaction forces between a particle and a wafer. We show that there is a simple correlation between particle deposition and the product of the zeta-potentials of the wafer and particle. This correlation can be explained by introducing the linear superposition approximation to the derivation of electrical double-layer interactions. The addition of surfactant will also decrease dispersion attraction, introduce steric repulsion, and eliminate adhesion force, as indicated by the results of surface force measurements. © 2003 The Electrochemical Society. All rights reserved.

Direct Surface Force Measurement of Particles from Micron to Nanosize

Direct Surface Force Measurement of Particles from Micron to Nanosize