Colloidal Probe Atomic Force Microscopy Research Articles

Quantifying and Decoupling Molecular Interactions of Ionic Liquids with Gold Electrodes.

This work combined gold colloid probe atomic force microscopy (AFM) with a quartz crystal microbalance (QCM) to accurately quantify the molecular interactions of fluorine-free phosphonium-based ionic liquids (ILs) with gold electrode surfaces. First, the interactions of ILs with the gold electrode per unit area (, N/m2) were obtained via the force-distance curves measured by gold probe AFM. Second, a QCM was employed to detect the IL amount to acquire the equilibrium number of IL molecules adsorbed onto the gold electrode per unit area (NIL, Num/m2). Finally, the quantified molecular interactions of ILs with the gold electrode (F0, nN/Num) were estimated. F0 is closely related to the IL composition, in which the IL with the same anion but a longer phosphonium cation exhibits a stronger molecular interaction. The changes in the quantified interactions of gold with different ILs are consistent with the interactions predicted by the extended Derjaguin-Landau-Verwey-Overbeek theory, and the van der Waals interaction was identified as the major contribution of the overall interaction. The quantified molecular interaction is expected to enable the direct experimental-derived interaction parameters for molecular simulations and provide the virtual design of novel ILs for energy storage applications.

Exploring the mechanisms of calcium carbonate deposition on various substrates with implications for effective anti-scaling material selection

The unexpected scaling phenomena have resulted in significant damages to the oil and gas industries, leading to issues such as heat exchanger failures and pipeline clogging. It is of practical and fundamental importance to understand the scaling mechanisms and develop efficient anti-scaling strategies. However, the underlying surface interaction mechanisms of scalants (e.g., calcite) with various substrates are still not fully understood. In this work, the colloidal probe atomic force microscopy (AFM) technique has been applied to directly quantify the surface forces between calcite particles and different metallic substrates, including carbon steel (CR1018), low alloy steel (4140), stainless steel (SS304) and tungsten carbide, under different water chemistries (i.e., salinity and pH). Measured force profiles revealed that the attractive van der Waals (VDW) interaction contributed to the attachment of the calcium carbonate particles on substrate surfaces, while the repulsive electric double layer (EDL) interactions could inhibit the attachment behaviors. High salinity and acidic pH conditions of aqueous solutions could weaken the EDL repulsion and promote the attachment behavior. The adhesion of calcite particles with CR1018 and 4140 substrates was much stronger than that with SS304 and tungsten carbide substrates. The bulk scaling tests in aqueous solutions from an industrial oil production process showed that much more severe scaling behaviors of calcite was detected on CR1018 and 4140 than those on SS304 and tungsten carbide, which agreed with surface force measurement results. Besides, high salinity and acidic pH can significantly enhance the scaling phenomena. This work provides fundamental insights into the scaling mechanisms of calcite at the nanoscale with practical implications for the selection of suitable anti-scaling materials in petroleum industries.

Rate dependence in adhesive particle–particle contacts affect ceramic suspension bulk flow behavior

Particle–fluid mixtures are known for displaying a wide variety of interesting flow mechanisms, such as thickening and thinning under shear. It is now becoming increasingly evident that even molecular scale effects are relevant for this macroscopic flow behavior of suspensions. Here we show that even 50μm ceramic beads in a non-density matched solvent are affected by the pH of the solvent. We trace the origin of the pH dependence to the contact mechanics using colloidal probe atomic force microscopy (CP-AFM). The gel-like structure of the pH 3 samples suggests that adhesion effects play a major role, but which adhesion timescale competes with shear rate to affect the rheology is not obvious. We test here two time scales in the contact mechanics: total contact time tc and contact retraction speed vr. We observe that contact time is the most important variable to correlate with rheology. The ceramic particle suspension so serves as a model system to help understand which adhesive mechanism affects flow behavior in the suspension.

Unsteady drag force on an immersed sphere oscillating near a wall

The unsteady hydrodynamic drag exerted on an oscillating sphere near a planar wall is addressed experimentally, theoretically and numerically. The experiments are performed by using colloidal-probe atomic force microscopy in thermal noise mode. The resonance frequencies and quality factors are extracted from the measurement of the power spectrum density of the probe oscillation for a broad range of gap distances and Womersley numbers. The shift in the resonance frequency of the colloidal probe as the probe goes close to a solid wall infers the wall-induced variations of the effective mass of the probe. Interestingly, a crossover from a positive to a negative shift is observed as the Womersley number increases. In order to rationalize the results, the confined unsteady Stokes equation is solved numerically using a finite-element method, as well as asymptotic calculations. The in-phase and out-of-phase terms of the hydrodynamic drag acting on the sphere are obtained and agree well with the experimental results. All together, the experimental, theoretical and numerical results show that the hydrodynamic force felt by an immersed sphere oscillating near a wall is highly dependent on the Womersley number.

Modulating particle-particle interaction in phyllosilicate serpentine aqueous suspensions using sodium citrate

The depletion of high-grade nickel sulfide ores has led to an increased interest in low-grade ultramafic ores, which are widely available but challenging to process due to their high content of phyllosilicate serpentine. The anisotropic surface charge and shape of serpentine particles lead to attractive interactions, which increase the viscosity of ore slurry and associated operational and equipment costs. To overcome this challenge, we investigate the application of an environmentally benign reagent, sodium citrate, to modify the particle-particle interactions in serpentine aqueous suspensions. Our results show that at alkaline pH (10), sodium citrate selectively adsorbs on the brucite plane of serpentine, making the entire particle overall negatively charged, which weakens the interparticle attraction and reduces the suspension's shear viscosity, yield stress, and storage modulus. We confirmed these results using colloidal probe atomic force microscopy (AFM) technique, which showed a significant weakening of attraction between silica and brucite surfaces upon the addition of citrate. This work enhances the understanding of surface interaction mechanisms of phyllosilicate serpentine particles in aqueous media with the addition of sodium citrate and provides useful implications for the application of green reagents in mineral operations involving phyllosilicate gangues. Our findings suggest that sodium citrate has great potential as an effective and sustainable reagent in the processing of abundantly available low grade ultramafic nickel ores.

Particle-Bubble Interactions: an Investigation of the Three-Phase Contact Line by Atomic Force Microscopy.

The dynamics of the three-phase contact line during particle-bubble interactions determine the stability of particle-bubble aggregates in flotation. The interaction of particles and sessile gas bubbles can be studied by colloidal probe atomic force microscopy (CP-AFM). This paper demonstrates a method to obtain the contact angle, the position of the three-phase contact line on the particle, and the bubble profile by utilizing the full information contained in AFM force-distance curves, i.e., force and CP-position information as well as the work done to move the three-phase contact line on the CP-particle. The proposed method does not require any assumption of a constant contact angle or a constant opening angle. This is achieved by the combined solution of the particle force balance and an expression for the work required to move the three-phase contact line over the colloid probe. The applicability to AFM force-distance measurements was demonstrated for the interaction of a hydrophobic SiO2 or a hydrophobic Al2O3 colloidal probe particle with sessile gas bubbles having radii between 45 and 80 μm.

Dissipation Mechanisms and Superlubricity in Solid Lubrication by Wet-Transferred Solution-Processed Graphene Flakes: Implications for Micro Electromechanical Devices.

Solution-processed few-layer graphene flakes, dispensed to rotating and sliding contacts via liquid dispersions, are gaining increasing attention as friction modifiers to achieve low friction and wear at technologically relevant interfaces. Vanishing friction states, i.e., superlubricity, have been documented for nearly-ideal nanoscale contacts lubricated by individual graphene flakes. However, there is no clear understanding if superlubricity might persist for larger and morphologically disordered contacts, as those typically obtained by incorporating wet-transferred solution-processed flakes into realistic microscale contact junctions. In this study, we address the friction performance of solution-processed graphene flakes by means of colloidal probe atomic force microscopy. We use a state-of-the-art additive-free aqueous dispersion to coat micrometric silica beads, which are then sled under ambient conditions against prototypical material substrates, namely, graphite and the transition metal dichalcogenides (TMDs) MoS2 and WS2. High resolution microscopy proves that the random assembly of the wet-transferred flakes over the silica probes results into an inhomogeneous coating, formed by graphene patches that control contact mechanics through tens-of-nanometers tall protrusions. Atomic-scale friction force spectroscopy reveals that dissipation proceeds via stick-slip instabilities. Load-controlled transitions from dissipative stick-slip to superlubric continuous sliding may occur for the graphene-graphite homojunctions, whereas single- and multiple-slips dissipative dynamics characterizes the graphene-TMD heterojunctions. Systematic numerical simulations demonstrate that the thermally activated single-asperity Prandtl-Tomlinson model comprehensively describes friction experiments involving different graphene-coated colloidal probes, material substrates, and sliding regimes. Our work establishes experimental procedures and key concepts that enable mesoscale superlubricity by wet-transferred liquid-processed graphene flakes. Together with the rise of scalable material printing techniques, our findings support the use of such nanomaterials to approach superlubricity in micro electromechanical systems.

Effect of Electrode Surface Chemistry on Ion Structuring of Imidazolium Ionic Liquids.

Surface chemistry plays a critical role in the ion structuring of ionic liquids (ILs) at the interfaces of electrodes and controls the overall energy storage performance of the system. Herein, we functionalized the gold (Au) colloid probe of an atomic force microscope with -COOH and -NH2 groups to explore the effect of different surface chemical properties on the ion structuring of an IL. Aided by colloid-probe atomic force microscopy (AFM), the ion structuring of an imidazolium IL, 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6], abbreviated as BP hereafter), on the Au electrode surface and the ion response to the change in the surface chemistry are investigated. AFM morphologies, contact angles, and approaching force-distance curves of the BP IL on the functionalized Au surfaces exhibited that the IL forms a more obvious layering structure on the -COOH-terminated Au surface (Au-COOH), while it forms heterogeneous and aggregating droplets on the -NH2 surface (Au-NH2). The formed uniform and aggregation-free ion layers in the vicinity of the Au-COOH surface are due to the π-π+ stacking interaction between the delocalized π+ electrons from the imidazolium ring in the IL [BMIM]+ cation and the localized π electrons from the sp2 carbon on the -COOH group. The in situ observation of nano-friction and torsional resonance frequency at the IL-electrode interfaces further demonstrated the ion structuring of the IL at Au-COOH, which results in a more sensitive electrochemical response associated with a faster capacitive process.

Effects of liquid surface tension on gas capillaries and capillary forces at superamphiphobic surfaces

The formation of a bridging gas capillary between superhydrophobic surfaces in water gives rise to strongly attractive interactions ranging up to several micrometers on separation. However, most liquids used in materials research are oil-based or contain surfactants. Superamphiphobic surfaces repel both water and low-surface-tension liquids. To control the interactions between a superamphiphobic surface and a particle, it needs to be resolved whether and how gas capillaries form in non-polar and low-surface-tension liquids. Such insight will aid advanced functional materials development. Here, we combine laser scanning confocal imaging and colloidal probe atomic force microscopy to elucidate the interaction between a superamphiphobic surface and a hydrophobic microparticle in three liquids with different surface tensions: water (73 mN m−1), ethylene glycol (48 mN m−1) and hexadecane (27 mN m−1). We show that bridging gas capillaries are formed in all three liquids. Force-distance curves between the superamphiphobic surface and the particle reveal strong attractive interactions, where the range and magnitude decrease with liquid surface tension. Comparison of free energy calculations based on the capillary menisci shapes and the force measurements suggest that under our dynamic measurements the gas pressure in the capillary is slightly below ambient.

Programmable Interactions of Cellulose Acetate with Octadecyltrichlorosilane-Functionalized SiO2 Nanoparticles

It is significant to understand the interfacial interactions involved between the cellulose acetate (CA) and dispersed nanomaterials, in which the enhanced interaction improves the mechanical behavior of CA. In this work, the amendments of CA with SiO2 nanoparticles have been found to be endowed by grafting varying concentrations (0, 3, 5, and 6%) of octadecyltrichlorosilane (OTS). Aided by SiO2 colloid probe atomic force microscopy (AFM with a probe diameter of 20 μm), the adhesion force between CA and SiO2 is found to be programmable by tuning OTS concentrations functionalized onto SiO2 surfaces. The adhesion forces of 5% OTS-functionalized SiO2 with CA are the strongest, followed by the ones of 0, 3, and 6% OTS, resulting in a smoother and denser morphology on the film with 5% OTS. The AFM-measured approaching force-distance curves have been further compared to predictions by the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory, in which the XDLVO force is summed as the Liftshitz-van der Waals force (FLW), the electrostatic double-layer force (FEL), and the acid-base interaction force (FAB). FLW and FEL do not change significantly with OTS concentrations functionalized onto SiO2. However, FAB is sensitive to the functionalized OTS concentration onto SiO2 and significantly contributes to the interaction force of the composite films with 5% OTS, promoting the formation of a smooth and dense surface feature with a considerable mechanical performance demonstrated by load-displacement curves from a nanoindenter. This is highly encouraging and suggests that nanomaterials can be incorporated into CA to effectively improve their mechanical compatibility by programming the interaction between the CA matrix and nanomaterials.

Critical analysis of adhesion work measurements from AFM-based techniques for soft contact

HypothesisThe work of adhesion is a thermodynamic quantity that is frequently measured by atomic force microscopy (AFM). Determination of the work of adhesion requires quasi-equilibrium measurements, where we address the question of to what extent atomic force microscopy qualifies for quasi-equilibrium measurements. ExperimentTo measure the work of adhesion, we combined soft colloidal probe AFM (SCP AFM) with reflection interference contrast microscopy (RICM). This allowed us to extract the work of adhesion either from the pull-off force or from the contact radius. With these methods, we investigated the adhesion behavior of poly(N-isopropylacrylamide) (PNIPAM) polymer brushes in the swollen and solvent-induced collapsed state by systematically analyzing contact radii and adhesive forces. FindingsIn the swollen state, the adhesion to the PNIPAM brush was fivefold larger and exhibited significant time dependencies when measured with SCP AFM. A strong rate dependence of the pull-off force method was indicative of a non-equilibrium process. In order to reliably determine the equilibrium work of adhesion, the contact radius method was found to be the better because it is not rate dependent. Our work highlights the important benefits of using optical measurements to determine the contact radius when deriving the works of adhesion between colloidal probes and polymer brush surfaces.

Precise quantification of nanoparticle surface free energy via colloidal probe atomic force microscopy

Interfacial interactions of nanoparticles (NPs) in colloids are greatly influenced by the NP surface free energy (SFE). Due to the intrinsic physical and chemical heterogeneity of the NP surface, measuring SFE is nontrivial. The use of direct force measurement methods, such as colloidal probe atomic force microscopy (CP-AFM), have been proven to be effective for the determination of SFE on relatively smooth surfaces, but fail to provide reliable measurements for rough surfaces generated by NPs. Here, we developed a reliable approach to determine the SFE of NPs by adopting Persson’s contact theory to include the effect of surface roughness on the measurements in CP-AFM experiments. We obtain the SFE for a range of materials varying in surface roughness and surface chemistry. The reliability of the proposed method is verified by the SFE determination of polystyrene. Subsequently, the SFE of bare and functionalized silica, graphene oxide, and reduced graphene oxide were quantified and validity of the results was demonstrated. The presented method unlocks the potential of CP-AFM as a robust and reliable method of the SFE determination of nanoparticles with a heterogeneous surface, which is challenging to obtain with conventionally implemented experimental techniques.

Mechanical response of a thick poroelastic gel in contactless colloidal-probe rheology

When a rigid object approaches a soft material in a viscous fluid, hydrodynamic stresses arise in the lubricated contact region and deform the soft material. The elastic deformation modifies in turn the flow, hence generating a soft-lubrication coupling. Moreover, soft elastomers and gels are often porous. These materials may be filled with solvent or uncrosslinked polymer chains, and might be permeable to the surrounding fluid, which further complexifies the description. Here, we derive the point-force response of a semi-infinite and permeable poroelastic substrate. Then, we use this fundamental solution in order to address the specific poroelastic lubrication coupling associated with contactless colloidal-probe methods. In particular, we derive the conservative and dissipative components of the force associated with the oscillating vertical motion of a sphere close to the poroelastic substrate. Our results may be relevant for dynamic surface force apparatus and contactless colloidal-probe atomic force microscopy experiments on soft, living and/or fragile materials, such as swollen hydrogels and biological membranes.

Nanoscale friction of biomimetic hair surfaces.

We investigate the nanoscale friction between biomimetic hair surfaces using chemical colloidal probe atomic force microscopy experiments and nonequilibrium molecular dynamics simulations. In the experiments, friction is measured between water-lubricated silica surfaces functionalised with monolayers formed from either octadecyl or sulfonate groups, which are representative of the surfaces of virgin and ultimately bleached hair, respectively. In the simulations, friction is monitored between coarse-grained model hair surfaces with different levels of chemical damage, where a specified amount of grafted octadecyl groups are randomly replaced with sulfonate groups. The sliding velocity dependence of friction in the simulations can be described using an extended stress-augmented thermally activation model. As the damage level increases in the simulations, the friction coefficient generally increases, but its sliding velocity-dependence decreases. At low sliding velocities, which are closer to those encountered experimentally and physiologically, we observe a monotonic increase of the friction coefficient with damage ratio, which is consistent with our new experiments using biomimetic surfaces and previous ones using real hair. This observation demonstrates that modified surface chemistry, rather than roughness changes or subsurface damage, control the increase in nanoscale friction of bleached or chemically damaged hair. We expect the methods and biomimetic surfaces proposed here to be useful to screen the tribological performance of hair care formulations both experimentally and computationally.

Active microrheology of protein condensates using colloidal probe-AFM

Protein condensates resulting from liquid–liquid phase separation have long been studied as bio-adhesives and coating materials for various applications. More recently, they are also being scrutinized as models for membraneless organelles in cells. Quantifying their interfacial mechanics and rheology at micrometer scales is vital for better understanding the physics underlying membraneless organelles in cells and for developing and improving technological applications of protein condensates. This study demonstrates how colloidal probe atomic force microscopy with an oscillating tip can be used to simultaneously investigate the interfacial mechanics and dynamic rheological properties of micro-scale protein condensates, formed via carefully controlled capillary condensation. This new approach can access oscillation frequencies ranging from 1 to 104 rad/s. By analyzing the data using an equivalent mechanical model, three characteristic frequency domains for the mechanics of micro-scale protein condensates are found: an interfacial tension-dominated domain at low frequencies, a transition domain (viscous-to-elastic crossover) at intermediate frequencies, and an elasticity-dominated domain at high frequencies, covering a broad range of time scales relevant in biology and technological applications of protein condensates.

Sliding Friction and Superlubricity of Colloidal AFM Probes Coated by Tribo-Induced Graphitic Transfer Layers.

Colloidal probe atomic force microscopy (AFM) allows us to explore sliding friction phenomena in graphite contacts of nominal lateral size up to hundreds of nanometers. It is known that contact formation involves tribo-induced material transfer of graphite flakes from the graphitic substrate to the colloidal probe. In this context, sliding states with nearly vanishing friction, i.e., superlubricity, may set in. A comprehensive investigation of the transfer layer properties is mandatory to ascertain the origin of superlubricity. Here we explore the friction response of micrometric beads, of different size and pristine surface roughness, sliding on graphite under ambient conditions. We show that such tribosystems undergo a robust transition toward a low-adhesion, low-friction state dominated by mechanical interactions at one dominant tribo-induced nanocontact. Friction force spectroscopy reveals that the nanocontact can be superlubric or dissipative, in fact undergoing a load-driven transition from dissipative stick-slip to continuous superlubric sliding. This behavior is excellently described by the thermally activated, single-asperity Prandtl-Tomlinson model. Our results indicate that upon formation of the transfer layer, friction depends on the energy landscape experienced by the topographically highest tribo-induced nanoasperity. We consistently find larger dissipation when the tribo-induced nanoasperity is slid against surfaces with higher atomic corrugation than graphite, like MoS2 and WS2, in prototypical van der Waals layered heterojunctions.

Tuning the surface functionality of polyamide films via termination reaction in molecular layer-by-layer deposition

Molecular layer-by-layer (mLbL) deposition of highly crosslinked polyamide-based membranes affords flexibility and control over membrane properties such as thickness, roughness, and chemistry of the selective membrane layer. Of particular interest is the ability to non-destructively tailor the surface chemistry of the membrane for a particular purpose, such as enhancing hydrophilicity or minimizing membrane fouling. Here, we show that the surface chemistry of the mLbL membrane can be tuned via termination reactions to render the surface rich in –COOH, −NH2, −polyethylene glycol (−PEG), or −fluorinated groups. We systematically characterize the resulting surfaces with X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) to validate successful modification and to ensure the low surface roughness is maintained, respectively. We then use pH-dependent contact angle and carboxylate-modified colloidal probe AFM to measure the surface wettability and adhesion of the modified surfaces. The measured adhesion force follows the ranking –NH2≫ −fluorinated > –COOH ≈ −PEG, where the –COOH and −PEG are repulsive due to charge interactions and hydration state, respectively. Combined with the low surface roughness afforded by mLbL deposition, surface functionalization through termination reactions as shown here will allow researchers to disentangle contributions of surface chemistry from surface roughness to the overall performance and fouling of polyamide-based membranes for water purification and advanced chemical separations.

Oscillatory structural forces probed by the nanofilm Macroscopic contact angle

The research on oscillatory structural forces (OSF) has a long history. OSF arise when liquid dispersions of a nano/micellar solution of complex fluids are confined between surfaces. In recent years, significant progress has been made in the measuring and modeling of OSF. Advanced techniques that use tools such as the surface forces apparatus (SFA), colloidal probe atomic force microscope (CP-AFM), and foam film capillary balance (FCB) were developed to gain information about nanofilm interactions in the confinement film geometry as the “layer” and “in-layer” particle entropy structural transition takes place. Henderson’s theory, based on the statistical mechanics approach to model the OSF, proposed analytical results using the Laplace transformation of the radial distribution function (RDF) for two large hard spheres in a fluid to calculate the film free energy; this approach is commonly applied to the model of the nanofilm layering between two solid surfaces. To extend Henderson’s theory to model the “layer” and “in-layer” structural transition of a capillary system, e.g., foam and emulsions, we propose the use of the foam film-meniscus macroscopic contact angle approach to calculate the nanofilm’s OSF.

Repulsive Interactions of Eco-corona-Covered Microplastic Particles Quantitatively Follow Modeling of Polymer Brushes.

The environmental fate and toxicity of microplastic particles are dominated by their surface properties. In the environment, an adsorbed layer of biomolecules and natural organic matter forms the so-called eco-corona. A quantitative description of how this eco-corona changes the particles' colloidal interactions is still missing. Here, we demonstrate with colloidal probe-atomic force microscopy that eco-corona formation on microplastic particles introduces a compressible film on the surface, which changes the mechanical behavior. We measure single particle-particle interactions and find a pronounced increase of long-range repulsive interactions upon eco-corona formation. These force-separation characteristics follow the Alexander-de Gennes (AdG) polymer brush model under certain conditions. We further compare the obtained fitting parameters to known systems like polyelectrolyte multilayers and propose these as model systems for the eco-corona. Our results show that concepts of fundamental polymer physics, like the AdG model, also help in understanding more complex systems like biomolecules adsorbed to surfaces, i.e., the eco-corona.

Contactless Rheology of Soft Gels Over a Broad Frequency Range

We report contactless measurements of the viscoelastic rheological properties of soft gels. The experiments are performed using a colloidal-probe atomic force microscope in a liquid environment and in dynamic mode. The mechanical response is measured as a function of the liquid gap thickness for different oscillation frequencies. Our measurements reveal an elastohydrodynamic coupling between the flow induced by the probe oscillation and the viscoelastic deformation of the gels. The data are quantitatively described by a viscoelastic lubrication model. The frequency-dependent storage and loss moduli of the polydimethylsiloxane gels are extracted from fits of the data to the model and are in good agreement with the Chasset-Thirion law. Our results demonstrate that contactless colloidal-probe methods are powerful tools that can be used for probing soft interfaces finely over a wide range of frequencies.