Surfactant boundary lubricant film modified by an amphiphilic diblock copolymer

The effect of the uptake of a low-molecular-weight amphiphilic diblock copolymer on the morphology of didodecyldimethylammonium bromide (DDAB) adsorbed layers on mica, the interactions between two coated surfaces, and the frictional properties of the boundary film have been studied using an atomic force microscope and a dynamic surface forces apparatus nanotribometer. When DDAB-coated surfaces in aqueous solution were compressed, hemifusion or removal of the adsorbed surfactant bilayers could not be induced, and no frictional force could be measured between the surfaces, which display superior lateral cohesion and lubricant properties. Coadsorbing octadecyl end modified poly(ethylene oxide) chains at low density facilitates hemifusion, generating significant shear stress and leading to stick-slip instabilities. The mixed films regain their lateral cohesion at higher adsorbed copolymer densities, but an extra short-range attraction brings the adsorbed layers into adhesive contact without causing bilayer hemifusion. Here, noticeable frictional forces are also measured.     

Application of colloid probe atomic force microscopy to the adhesion of thin films of viscous and viscoelastic silicone fluids

The adhesive characteristics of thin films (0.2-2 μm) of linear poly(dimethylsiloxane) (PDMS) liquids with a wide range of molecular weights have been measured using an atomic force microscope with a colloid probe (diameters 5 and 12 μm) for different separation velocities. The data were consistent with a residual film in the contact region having a thickness of ～6 nm following an extended dwell time before separation of the probe. It was possible to estimate the maximum adhesive force as a function of the capillary number, Ca, by applying existing theoretical models based on capillary interactions and viscous flow except at large values of Ca in the case of viscoelastic fluids, for which it was necessary to develop a nonlinear viscoelastic model. The compliance of the atomic force microscope colloid beam was an important factor in governing the retraction velocity of the probe and therefore the value of the adhesive force, but the inertia of the beam and viscoelastic stress overshoot effects were not significant in the range of separation velocities investigated.     

AFM study of the stability of a dense affinity-bound liposome layer

Liposomes that are surface-bound to a biomaterial such as a contact lens are of interest for localized delivery of therapeutic agents, but it is not known whether such liposome layers are sufficiently robust. The stability of a dense, PEG-functionalized layer of liposomes, affinity-bound onto a multilayer coated surface, was tested under various stress conditions using colloid-probe atomic force miscroscopy (AFM). The different stress effects were generated by varying the applied normal load of the probe and the impinging fluid shear through different approach velocities and by varying the applied lateral forces by scanning under increasing force loads. The effect of applied forces (normal and lateral) was further investigated by coating the probe with a layer of albumin. The liposomes remained intact following the ramping of both protein-coated and uncoated probes under the normal and lateral loads. The low-fouling nature of these liposomes, with respect to nonspecific protein adsorption, was also demonstrated from the interaction force measurements which showed only weak adhesion from the protein layer during the contact period of the albumin-coated probe. The observed adhesive interactions were concluded to be a direct result of the applied load from the probe, during the force measurements, rather than from attraction of the protein molecules for the surface-bound liposomes. The low frictional response of the liposome layer indicated the viscoelastic nature of these molecules, which enabled liposome structure retention during the continuous load application. The demonstrated stability of the liposomes presents a system of viable and localized drug delivery in, for example, ophthalmic applications.     

Quantification of particle-bubble interactions using atomic force microscopy: A review

The attachment of particles to bubbles in solution is of fundamental importance to several industrial processes, most notably in the process of froth flotation. During this process hydrophobic particles attach to air bubbles in solution, which allows them to be separated as froth at the surface. The addition of chemicals can help to modulate these interactions to increase the yield of the minerals of interest. Over the past decade the atomic force microscope (AFM) has been adapted for use in studying the forces involved in the attachment of single particles to bubbles in the laboratory. This allows the measurement of actual DLVO (Derjaguin, Landau, Vervey and Overbeek) forces and adhesive contacts to be measured under different conditions. In addition contact angles may be calculated from features of force versus distance curves. It is the purpose of this article to illustrate how the colloid probe technique can be used to make single particle-bubble interactions and to summarise the current literature describing such experiments.     

Contribution of relaxation processes to adhesive-joint strength of viscoelastic polymers

Relaxation processes accompany all stages of the lifetime of viscoelastic pressure-sensitive polymer adhesives, which can form strong adhesive joints with substrates of various chemical natures under application of a slight external pressure to the adhesive film for a few seconds. This review deals with comparison of the adhesion and relaxation properties of a number of typical pressure-sensitive adhesives based on polyisobutylene, butyl rubber, styrene-isoprene-styrene triblock copolymers, alkyl acrylate copolymers, and silicone adhesives as well as pressure-sensitive adhesives based on blends of high-molecular-mass polyvinylpyrrolidone with oligomeric poly(ethylene glycol). Within all three stages of the lifetime of adhesive joints (under adhesive-bond-forming pressure, upon withdrawal of contact pressure in the course of relaxation of the adhesive material, and under the force detaching an adhesive film from the substrate surface), the strength of adhesive joints has been shown to be controlled by large-scale relaxation processes, which are characterized by long relaxation times in the range 150–800 s. All examined pressure-sensitive adhesives can be arbitrarily divided into two groups. The first group is composed of fluid adhesives that relax comparatively fast and exhibit no residual (unrelaxed) stress. The second group includes elastic adhesives capable storing mechanical energy in the course of deformation that are characterized by appreciably longer relaxation times and display residual stress after relaxation. Conditions of adhesive debonding (e.g., strain amplitude and deformation velocity) significantly affect the relaxation process.     

Quasi-static electrorheological properties of hematite/silicone oil suspensions under DC electric fields

In this work, a modified rheometer has been used to gain information on the "start-up" of the shear flow of an electrorheological (ER) fluid consisting of hematite particles dispersed in silicone oil. The results show that unelectrified suspensions behave essentially as fluids, continuously deforming upon application of shear. However, this behavior changes in the presence of an electric field. For low fields and low volume fractions of solids, a solidlike (drastic increase in shear stress after the strain is applied) behavior is observed for small deformations. If the strain is increased, the yield starts and a transition to a viscoelastic-plastic nature is observed. Finally, a plastic behavior is characteristic of the post-yield regime. If the field strength and solids content are high, a discontinuous flow profile develops. These results, together with direct structural observations, suggest that the observed behavior is compatible with the formation of layers of particles electrophoretically deposited on the electrodes; the layers turn into rings when the shear field is applied. It is the slip of the fluid between these rings that can be considered responsible for the ER effect in these suspensions.     

Nanoscale high-frequency contact mechanics using an AFM tip and a quartz crystal resonator

The transmission of high-frequency shear stress through a microscopic contact between an AFM tip and an oscillating quartz plate was measured as a function of vertical pressure, amplitude, and surface properties by monitoring the MHz component of the tip's deflection. For dry surfaces, the transmission of shear stress is proportional to the vertical load across the contact. This provides a measure of the forces of adhesion between the substrate and the tip. When stretching soft polymeric fibers created by pulling on the surface of a pressure sensitive adhesive, the transmitted shear stress decreased linearly with extension over the entire range of pulling. This contrasts with the static adhesive force, which remained about constant until it discontinuously dropped at the point of rupture.     

Simulation of the Adhesion of Particles to Surfaces

The removal of micrometer and submicrometer particles from dielectric and metal films represents a challenge in postchemical mechanical polishing cleaning. Proper modeling of the adhesive force between contaminant particles and these films is needed to develop optimal solutions to postchemical mechanical polishing cleaning. We have previously developed and experimentally validated a model to describe the adhesion between spherical particles and thin films. This simulation expands previous models to characterize the adhesive interaction between asymmetrical particles, characteristic of a polishing slurry, and various films. Our simulation accounts for the contact area between particles and substrates, as well as the morphology of the surfaces. Previous models fail to accurately describe the contact of asymmetrical particles interacting with surfaces. By properly accounting for nonideal and geometry and morphology, the simulation predicts a more accurate adhesive force than predictions based upon an ideal van der Waals model. The simulation is compared to experimental data taken for both semi-ideal particle-substrate systems (polystyrene latex spheres in contact with silicon films) and asymmetrical systems (alumina particles in contact with various films). Copyright 2001 Academic Press.     

Targeted particulate adhesion to cellulose surfaces mediated by bifunctional fusion proteins

The adhesion of particles to surfaces is an integral element in many commercial and biological applications. In this article, we report on the direct measurements of protein-mediated deposition and binding of particles to model cellulose surfaces. This system involves a family of heterobifunctional fusion proteins that bind specifically to both a red dye and cellulose. Amine-coated particles were labeled with a red dye, and a fusion protein was attached to these particles at various number densities. The strength of adhesion of a single particle to a cellulose fiber was measured using micropipette manipulation as a function of the specificity of the protein and its surface density and contact time. The frequency and force of adhesion were seen to increase with contact time in fiber experiments. The dynamics of adhesion of the functionalized particles to cellulose-coated glass slides under controlled hydrodynamic flow was explored using a flow chamber for two scenarios: detachment of bound particles and attachment of particles in suspension as a function of the shear rate and surface density of protein. Highly specific adhesion was observed. The critical shear rate for particle detachment was an increasing function of cellulose binding domain (CBD) density on particle surface. A rapid irreversible attachment of particles to cellulose was observed under flow. Using a family of proteins that were divalent for binding either the red dye or cellulose, we found that particle detachment occurred because of the failure of the cellulose-CBD bond. A comparison of fiber binding and particle detachment results suggests that forces of adhesion of particles to cellulose of up to 2 nN can be obtained with this molecular system through multiple interactions. This study, along with the adhesion simulations currently under development, forms the basis of particulate design for specific adhesion applications.     

Investigation of shear failure mechanisms of pressure‐sensitive adhesives

We report new experiments investigating the failure mechanisms in shear, of thin layers of acrylic pressure‐sensitive adhesives (PSA). We have developed a novel experimental device able to shear a soft adhesive layer confined between a rigid hemispherical lens and a rigid glass substrate. Using the resources of in situ contact visualization, the nonhomogeneous deformation of the layer and the shear failure processes were observed optically. Depending on the rheological properties of the adhesive, ratios of the contact radius over the layer thickness of 10–30 were achieved, mimicking well the contact conditions encountered in a thin adhesive layer within a joint. When the adhesive was weakly crosslinked, we observed a fluid‐like behavior and could measure a reasonable value for the viscosity of the PSA, implying that flow can occur in the layer and failure will occur by creep. On the other hand, for a more crosslinked adhesive, closer to what is used in applications, a stick‐slip peeling behavior was observed, which involves a coupling between peeling mechanisms at the leading edge of the contact and interfacial slippage. Such a process suggests a failure by fracture rather than by creep. Interestingly, the peeling mechanisms and the associated stress levels change significantly when the layer becomes as thin as 20 μm, implying a fracture process that is controlled by a critical energy release rate in shear G_IIc rather than by a critical shear stress causing failure of the interfacial bonds. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3316–3330, 2005     

Direct measurement of interactions between stimulation-responsive drug delivery vehicles and artificial mucin layers by colloid probe atomic force microscopy

A novel thermo- and pH-sensitive nanogel particle, which is a core-shell structured particle with a poly(N-isopropylacrylamide) (p(NIPAAm)) hydrogel core and a poly(ethylene glycol) monomethacrylate grafted poly(methacrylic acid) (p(MMA-g-EG)) shell, is of interest as a vehicle for the controlled release of peptide drugs. The interactions between such nanogel particles and artificial mucin layers during both approach and separation were successfully measured by using colloid probe atomic force microscopy (AFM) under various compression forces, scan velocities, and pH values. While the magnitudes of the compression forces and scan velocities did not affect the interactions during the approach process, the adhesive force during the separation process increased with these parameters. The pH values significantly influenced the interactions between the nanogel particles and a mucin layer. A large steric repulsive force and a long-range adhesive force were measured at neutral pH due to the swollen p(MMA-g-EG) shell. On the other hand, at low pH values, the steric repulsive force disappeared and a short-range adhesive force was detected, which resulted from the collapse of the shell layer. The nanogel particles possessed a pH response that was sufficient to protect the incorporated peptide drug under the harsh acidic conditions in the stomach and to effectively adhere to the mucin layer of the small intestine, where the pH is neutral. The relationships among the nanogel particle-mucin layer interactions, pH conditions, scan velocities, and compression forces were systemically investigated and discussed.     

Stick slip contact mechanics between dissimilar materials: effect of charging and large friction

Measurements of the contact radius as a function of applied force between a mica surface and a silica surface (mica/silica) in air are reported. The load/unload results show that the contact radius generally increases with applied force. Because of the presence of charging due to contact electrification, both a short-range van der Waals adhesion force and longer-range electrostatic adhesive interaction contribute to the measured force. The results indicate that approximately 20% of the pull-off force is due to van der Waals forces. The contact radius versus applied force results can be fit to Johnson-Kendall-Roberts (JKR) theory by considering that only the short-range van der Waals forces contribute to the work of adhesion and subtracting a constant longer-range electrostatic force. Also, an additional and unexpected step function is superimposed on the contact radius versus applied force curve. Thus, the contact diameter increases in a stepped dependence with increasing force. The stepped contact behavior is seen only for increasing force and is not observed when symmetric mica/mica or silica/silica contacts are measured. In humid conditions, the contact diameter of the mica/silica contact increases monotonically with applied force. Friction forces between the surfaces are also measured and the shear stress of a mica/silica interface is 100 times greater than the shear stress of a mica/mica interface. This large shear stress retards the increase in contact area as the force is increased and leads to the observed stepped contact mechanics behavior.     

The role of the pressing-on in the adhesion of elastic particles

One has carried out an analysis of the influence of the preliminary pressing-on on components of the adhesion force of different natures for the case of the contact of elastic particles with a rigid substrate. Two pressing-on variants are considered; as, - those realized under the effect of a dynamic and a static load. It has been shown that an increase in the adhesion of elastic particles to the surface resulting from the preliminary pressing-on is attributable to an increase in the adhesion force component due to a double electric layer in contact.     

Colloidal aggregate micromechanics in the presence of divalent ions

Colloidal gels exhibit rheological properties, such as a yield stress and elasticity, which arise from the manner in which stress is transmitted through the microstructure. Insight into the mechanisms of stress transmission is critical in developing a full understanding of the mechanics of these materials. Paramount to this is a thorough knowledge of the interparticle interactions. In this work, we use optical trapping to study interactions between poly(methyl methacrylate) (PMMA) particles in adhesive contact by measuring the bending elasticity of directly assembled colloidal aggregates under various physicochemical conditions. The simplified geometry of the aggregate enables us determine the single-bond rigidity, which can then be related to the work of adhesion, W(SL), through the Johnson-Kendall-Roberts (JKR) theory of adhesion. We find that W(SL) is independent of ionic strength in flocculating monovalent salt solutions. However, more complex behavior is observed for divalent salts. Using zeta-potential measurements, we show that divalent cations adsorb to the particle surface. This results in the formation of ionic bridges between particles in adhesive contact. A model of the aggregate micromechanics that considers the divalent ion contribution to the surface energy provides a direct link between the interfacial properties of the particles, nanoscale contact interactions between particles, and the bulk gel modulus.     

Stress jumps on weakly flocculated dispersions: steady state and transient results

Weakly flocculated, thixotropic suspensions have been investigated by means of fast stress jump experiments. With a suitable procedure, reliable stress relaxation data could be collected starting 20 ms after cessation of flow. This technique has been used to determine the elastic and hydrodynamic contributions to the shear stress. Steady state as well as transient flows have been studied for suspensions containing either fumed silica or carbon black particles in a Newtonian medium. In both systems, the elastic stress totally dominates the response at low shear rates and consequently also the apparent yield stress. This stress contribution becomes negligibly small at high shear rates. The hydrodynamic contribution to the viscosity has finite limits at both the low and high shear rate ends. The data are relevant for testing rheological models. As an illustration, it is shown that the data agree qualitatively with the model proposed by Potanin et al. (J. Chem. Phys. 102 (14) (1995) 5845-5853).     

Cooperativity of Catechols and Amines in High-Performance Dry/Wet Adhesives

The outstanding adhesive performance of mussel byssal threads has inspired materials scientists over the past few decades. Exploiting the amino-catechol synergy, polymeric pressure-sensitive adhesives (PSAs) have now been synthesized by copolymerizing traditional PSA monomers, butyl acrylate and acrylic acid, with mussel-inspired lysine- and aromatic-rich monomers. The consequences of decoupling amino and catechol moieties from each other were compared (that is, incorporated as separate monomers) against a monomer architecture in which the catechol and amine were coupled together in a fixed orientation in the monomer side chain. Adhesion assays were used to probe performance at the molecular, microscopic, and macroscopic levels by a combination of AFM-assisted force spectroscopy, peel and static shear adhesion. Coupling of catechols and amines in the same monomer side chain produced optimal cooperative effects in improving the macroscopic adhesion performance.     

Optimal shapes for adhesive binding between two elastic bodies

The pull-off force required to separate two elastic bodies in adhesive binding depends on the surface shapes of the corresponding binding regions on the two bodies. Given a fixed binding area A, the optimal shapes are those which give the maximum pull-off force sigma(th)A where sigma(th) is the theoretical strength of interactive forces between the two solids. Here we study closed form solutions to the optimal shapes for adhesive binding over a small circular region where slip is allowed whenever shear stress along the contact interface exceeds a critical value.     

Tailoring the interfacial assembly of colloidal particles by engineering the mechanical properties of the interface

Fluid interfaces can be used as a platform for promoting the direct and spontaneous self-assembly of colloidal particles, where the driving force is the reduction in interfacial energy. In addition, fluid interfaces allow fine-tuning of the particles ensemble by an external force, such as the presence of an imposed interfacial flow, or by engineering the interparticle interactions dictated by the interplay of interfacial forces. As a consequence, a wide-ranging set of interfacial structures can be achieved from liquid-like layers, which can flow under stress, to amorphous solids that are able to sustain static stress. Here, far from a comprehensive overview of the interfacial assembly of colloidal particles, different ways of tailoring it by rationally designing the rheological properties of the interface are provided, with a focus on experimental and theoretical methods and model systems that have been recently exploited. In particular, ligand-coated nanoparticles, with a strong emphasis on the effect of the ligands on the interfacial structure and the rheological properties, and soft nanogel particles, in which an environmental factor, such as the temperature, drives to different interfacial structures and mechanical responses will be further discussed.     

Static Yield Stress of an Electro-Rheological Fluid

The static yield stress of an electro-rheological fluid (starch/gas-oil and mesophase-carbon/gas-oil, abbreviated as ERF), congealed by an electric field, has been examined by means of a tensile tester with parallel electrodes. Static yield stress showed different behavior from dynamic yield stress reported by many investigators: thus static yield stress is proportional to applied field strength, but not to the square of it, as is dynamic yield stress. The adhesive force between the particles was not Coulomb's force but Maxwell's force. The theory of McLean and Ikazakiet al.using the Johnsen–Rahbeck effect on the adhesive force of the dust pile on an electrode of the electro-static precipitator was applied and the deduced equation actually explained the phenomena. It was clarified experimentally and theoretically that the physical properties of the ERF particles had no effect on the adhesive force of the pearl chains of a congealed ERF; on the contrary, the volumetric concentration did affect it.     

RECENT PROGRESS OF NANO-MECHANICAL MAPPING

 Nano-mechanical mapping by atomic force microscopy has been developed as an useful application to measure mechanical properties of soft materials at nanometer scale. To date, the Hertzian theory was used for analyzing force-distance curves as the simplest model among several contact mechanics between elastic bodies. However, the preexisting methods based on this theory do not consider the adhesive interaction in principle, which cannot be neglected in the ambient condition. A new analytical method was introduced to estimate the elasticity and the adhesive energy simultaneously by means of the JKR theory, describing adhesive contact between elastic materials. Poly(dimethylsiloxane) (PDMS) and isobutylene-co-isoprene rubber (IIR) were analyzed to verify the applicable limit of the JKR analysis. For elastic samples such as PDMS, the force-deformation plots obtained experimentally were consistent with JKR theoretical curves. Meanwhile, for viscoelastic samples, especially for IIR, the experimental plots revealed large deviations from JKR curves depending on scanning velocity and maximum loading force. Some nano-rheological arguments were employed based on the difference between these specimens.