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Dual-responsive poly-(N-isopropylacrylamide) (PNIPAM) microgels surface-functionalized with polyethylene glycol (PEG) or poly-2-dimethylaminoethyl methacrylate (PDMAEMA) were developed to enable the swelling behavior and surface properties of the microgels to be tuned independently. The thermo-triggered swelling and pH-triggered surface properties of the microgels were investigated in aqueous suspensions using dynamic light scattering and on substrates using the surface forces apparatus. Grafting polymer chains on the microgel surface did not impede the thermo-triggered swelling behavior of the microgels in suspensions and immobilized on substrates. An unprecedented decoupling of the swelling behavior and surface properties could be obtained. More particularly, the thermo-triggered swelling behavior of the PNIPAM underlying microstructure could be tuned below and above the phase transition temperature with no change in the surface potential and adhesion provided by the surface non-responsive PEG.

Normal and friction forces between immobilized two-dimensional (2D) homogeneous non-close-packed colloidal arrays made of different particles are compared in aqueous media. Soft pH-responsive (microgels) and nonresponsive hard (silica) particles of different sizes were used to create the 2D arrays. The results show that the friction of soft responsive structured layers can be successfully modulated by varying the pH, with a friction coefficient varying by nearly 3 orders of magnitude (10–2 to 1). This important change in lubricating properties is mainly correlated with the particle swelling behavior, i.e., the friction coefficient decreasing exponentially with an increase in the swelling ratio regardless of the size, surface coverage, and degree of ionization of the particles. In addition, the robustly attached microgel particles were able to sustain high pressure (up to 200 atm) without significant surface damage. The 2D arrays of nonresponsive hard particles also gave rise to a very low friction coeffic...

The tribological properties of two novel biomimetic multihierarchical polymers, synthesized by covalently linking single bottlebrush polymers onto a hyaluronic acid (HA) backbone, were investigated in the boundary lubrication regime using the surface forces apparatus. The polymers were immobilized on flat substrates, and their lubrication properties and wear resistance were investigated in aqueous media in the absence of a polymer reservoir (i.e., no free polymer chains in the surrounding medium) in order to better reveal the underlying mechanism of surface-attached biomimetic polymers. The effects of composition, structure, and, more particularly, surface attachment (physisorbed vs chemisorbed) on the tribological properties were investigated and compared with other biomimicking systems reported in the literature. The covalently surface attached bottlebrushes allowed wear resistance between sliding surfaces to be significantly improved, compared to physisorbed bottlebrushes, with a constant coefficient of friction (10

International audience; In this work, we have investigated the behavior under shear and compression of mica surfaces coated with poly(N-isopropylacrylamide) cationic microgels. We have observed the emergence of velocity dependent, shear-induced normal forces, which can be large enough to entrain a fluid film that separates the surfaces out of contact, driving the dynamic system from conditions of boundary to hydrodynamic lubrication. By implementing a feedback-loop control on the surface separation, we were able to quantify the magnitude of the lift force as a function of the surface separation and driving speed. Our results illustrate how elastohydrodynamic effects can play an important role in the lubrication of compliant surfaces, providing pathways for control of friction and wear.

We describe how a long-range repulsive interaction can surreptitiously modify the effective geometry of approaching compliant surfaces, with significant consequences on friction. We investigated the behavior under shear and compression of mica surfaces coated with poly(N-isopropylacrylamide) pNIPAM-based cationic microgels. We show that local surface deformations as small as a few nanometers must be considered to understand the response of such surfaces under compression and shear, in particular when the range of action of normal and friction forces are significantly different, as is often the case for macromolecular lubrication. Under these conditions, a subtle interplay between normal forces and surface compliance may significantly reduce friction increment by limiting the minimum approach of the surfaces under pressure. We found that stiffening of compressed microgels confined in the region of closest approach make it increasingly difficult to reduce the gap between the mica surfaces, limiting the defo...

Controlling surface coverage and stability of supported aminoalkylsilane monolayers on silica-based substrates still remains a challenge for the development of biosensors and nanomaterials. We have developed protocols using simple surface chemistry and self-assembly from solution without stringent deposition conditions to covalently attach monolayers of 11-aminoundecyltriethoxysilane (AUTES) onto mica and silica substrates. The resulting self-assembled monolayers (SAMs) exhibited excellent hydrolytic stability. The long alkyl chain together with the large grafting density and homogeneity enhanced the monolayer stability by preventing the Sisilane O Sisurface bonds from hydrolysis over a wide range of pH values (2–10) for long time periods (up to 8 days). The control over the surface density of amino groups was achieved and the reactivity of the amino SAMs was confirmed by covalently attaching carboxyl-functionalized nanoparticles on the SAMs. The immobilized nanoparticles exhibited the same hydrolytic stability as that of the SAMs. The AUTES SAMs prepared in this study exhibited the best hydrolytic stability of similar systems reported so far.

We report the first successful preparation of polyelectrolyte brushes using an ATRP initiator that was covalently grafted to silica and mica substrates via an organophosphonic acid. Covalent attachment of the initiator to silica and mica and the subsequent synthesis of polyacrylic acid (PAA) and poly(sulfopropyl methacrylic acid) brushes by water mediated-ATRP were confirmed by ATR-FTIR, ellipsometry, AFM, and contact angle measurements. The initiator–substrate bond was robust and could resist a large range of pH in the absence of salt. Interactions between PAA brushes anchored to mica via the organophosphonic acid initiator were investigated using a surface forces apparatus. The results confirmed the robustness of the initiator–mica bond as the brushes could resist shearing and compression under relatively high applied loads.

The frictional properties of a thin hexadecane film confined between two atomically smooth surfaces of mica were studied using the surface forces apparatus equipped with a 3D actuator-sensor attachment specially designed to investigate static and dynamic forces in three orthogonal directions simultaneously. The use of this attachment allows the relative alignment of the reciprocal sliding motion to be changed by an angle of 90 while maintaining the film under the same confinement conditions. The effects of the commensurability of the confining mica surfaces as well as the relative sliding direction on the frictional behavior of the hexadecane film were determined for different temperatures (18-29 C) and sliding velocities (4 nm/s to 4 μm/s). The confined hexadecane film exhibited smooth sliding friction whose amplitude increased with the commensuration of the surfaces. A progressive evolution in the kinetic friction force toward a steady-state value was observed over reciprocal sliding motion for given experimental conditions of applied load, sliding velocity and environmental temperature. This friction evolution shows to be dependent on the sliding history of the film and could result from a partial molecular ordering, occurring during shear. Refereed/Peer-reviewed

Summary: Unprecedented direct polymerization of sodium acrylate (NaA) on mica and silica substrates was undertaken using standard ATRP polymerization conditions at room temperature. The resulting thickness of the poly(sodium acrylate) (PNaA) grafted layer was determined using ellipsometry and AFM.

Poly(acrylic acid) (PAA) and poly(tert-butyl acrylate) (PBA) brushes of various grafting densities were prepared via surface-initiated polymerization of tert-butyl acrylate on mica. PAA was prepared by hydrolyzing the PBA brushes. The swelling behavior of PBA and PAA brushes was studied as a function of grafting density by AFM. The swelling of the polymer layer was found to be higher for PAA in water than for the PBA sample swollen with DFM.

A biofunctionalized graphene oxide (GO) nanosheet with improved physicochemical properties is useful for electrocatalysis and sensor development. Herein, a new class of functionalized GO with a chemically anchored biomolecule glucosamine is developed. Structural and chemical analyses confirm the glucosamine anchoring. Ultraviolet irradiation transforms the surface chemistry of GO. Glucosamine-anchored GO nanosheets exhibit improved cyclic voltammetric and amperometric sensing activity toward the model redox probe, ruthenium(II) and N-acetylneuraminic acid, respectively. The biomolecular anchoring and ultraviolet irradiation helped to tune and enhance the properties of GO, which may find multiple applications in optimizing sensor platforms.

Dynamic shear oscillation measurements at small strains are used to characterize the polymerization process in situ and the viscoelastic properties of cross-linked polyacrylamide hydrogels. Hydrogels are synthesized by free-radical redox polymerization of acrylamide (8 wt %) for different concentrations of cross-linker, N,N‘-methylenebis(acrylamide) (BIS), at different temperatures. Both elastic modulus G‘ and viscous modulus G‘‘ are measured in real time during the gelation which takes place directly between parallel rheometer plates. The elastic modulus G‘ remains constant with frequency, G‘(ω) ≈ cte, and is significantly larger than G‘‘(ω), characteristic of a well-developed cross-linked polymer network. Temperature scanning of the elastic modulus shows that G‘(T) is a linear relationship with a proportionality value that depends on the polymerization temperature Tpol. This observation is in agreement with the classical theory of rubberlike elasticity, i.e., G‘ = neRT where ne is the active network lin...

We studied the association of hydrophobically anchored polyelectrolyte layers with a free oppositely charged surfactant at a hydrophobized solid–liquid interface under partially screened conditions using the surface forces and ellipsometry techniques. Combining results from both measurements, we conclude that the association of surfactant (from solution below the cmc) with partially screened adsorbed polyelectrolyte layers causes a reduction in the surface density of the polymer chains and a subsequent reduction in the extensibility of the chains.

The texture of food is considered related to its rheological behavior when confined within thin films between two shearing or squeezing surfaces. Such thin-film tribological properties may represent foods undergoing massive grinding and deformation during mastication. The thin-film tribological properties rather than the bulk rheological properties correlated with the composition (oil droplets, etc.) and texture of mayonnaise samples. Using the Surface Forces Apparatus (SFA) technique and optical interferometry using fringes of equal chromatic order, we characterized the thin-film morphology and measured tribological and other interfacial properties of mayonnaise emulsions. Results revealed new properties that help differentiate between full fat, light and fat free mayonnaises. This provides an important approach to determine properties of such foods in thin films which cannot be deduced from bulk properties.

14 pages; International audience; We have studied the adsorption and lubricant properties of a multifunctional triblock copolymer poly(L-lysine)-b-poly(acrylic acid)-bpoly(L-lysine). In particular, we investigated the nature of the layer adsorbed under different conditions of polymer and salt concentration and the lubricant properties of the polymer layer before and after its chemical crosslinking by bridging the poly(acrylic acid) blocks. We found that the amount of polymer adsorbed is controlled by the ionic strength and the polymer concentration in the solution. In all cases, the self-assembled polymer layer is a poor lubricant before cross-linking, but the cohesion and load-carrying ability of the layer are substantially improved by this reaction. However, the chemically cross-linked coating has a limited deformation capacity as a consequence of its permanent network nature, and irreversible damage is observed after excessive strain of the film.

A new 3D sensor-actuator attachment for a Surface Forces Apparatus (SFA) allows measurements of friction forces between surfaces in all 3 orthogonal directions. The anisotropic friction forces when shearing two mica surfaces separated by a nanometer-thin film of hexadecane can induce complex transient and steady-state motions involving displacements perpendicular to the applied force and nonzero velocity at all stages of back-and-forth sliding. Refereed/Peer-reviewed

Static and dynamic interaction forces between two thermosensitive polymeric nanoparticle monolayers grafted onto mica surfaces and immersed in water were studied using a surface forces apparatus. The polymeric nanoparticles (NPs) were made of N,N-diethylacrylamide and had a hydrodynamic diameter of ca. 780 nm at 20 °C in aqueous suspension. They were irreversibly grafted onto chemically modified mica surfaces at a constant surface coverage of 2.6 NPs/µm2. The measured normal forces between two opposing NP monolayers were found to be strongly dependent on the temperature. At temperatures lower than the lower critical solution temperature (LCST), the grafted NPs were swollen, and the normal interaction forces between the two NP monolayers were repulsive. Above the LCST, the NPs collapsed, and attractive forces between the NP layers were measured. The swollen NPs were found to exhibit very low friction forces compared to the collapsed ones. The effect of the sliding velocity on the shear stress was investigated, and the results are in agreement with the so-called adhesive friction model developed for rubber friction. Our results suggest that the water content in the contact area and the interdiffusion of polymer chains are important parameters in determining the friction between polymer-bearing surfaces. Refereed/Peer-reviewed

The controlled grafting density of poly(tert-butyl acrylate) was studied on OH-activated mica substrates via surface-initiated atom-transfer radical polymerization (ATRP). By properly adjusting parameters such as the immobilization reaction time and the concentration of an ATRP initiator, a wide range of initiator surface coverages and hence polymer densities on mica were possible. The covalently immobilized initiator successfully promoted the polymerization of tert-butyl acrylate on mica surfaces. The resulting polymer layer thickness was measured by AFM using a step-height method. Linear relationships of the polymer thickness with respect to the molecular weight of the free polymer and with respect to the monomer conversion were observed, suggesting that ATRP is well controlled and relatively densely end-grafted layers were obtained. The polymer grafting density controlled by adjusting the initiator surface coverage was confirmed by the polymer layer swelling capacity and film thickness measurements.

Normal and lateral forces between two opposing monolayers of grafted polymer nanoparticles (NPs) were measured using the Surface Forces Apparatus in a humid atmosphere. The NPs made of N, N-diethylacrylamide and 2-hydroxyethyl methacrylate have a hydrodynamic diameter of ca. 660 nm at 25 degrees C. The effect of surface roughness was studied by creating surface asperities using different NP grafting densities ranging from 0.41 to 2.63 NPs/mum (2). An increase in the NPs grafting density gave rise to an increase in surface roughness and to a deformation of the nanoparticles caused by the lateral pressure between neighboring particles. An elastoplastic behavior of the nanoparticles was observed for large grafting densities, while a purely elastic behavior was observed for small grafting densities. The lateral forces measured between two opposing NP monolayers sliding past each other followed Amontons' law for all grafting densities. The friction coefficient between the surfaces appeared to increase significantly with an increase in surface roughness, which was inherent to an increase in the elastoplastic behavior of the NP monolayers.

Normal and shear forces were measured as a function of surface separation, D, between hydrophobized mica surfaces bearing layers of a hydrophobic-polyelectrolytic diblock copolymer, poly(methyl methacrylate)- block-poly(sodium sulfonated glycidyl methacrylate) copolymer (PMMA- b-PSGMA). The copolymers were attached to each hydrophobized surface by their hydrophobic PMMA moieties with the nonadsorbing polyelectrolytic PSGMA tails extending into the aqueous medium to form a polyelectrolyte brush. Following overnight incubation in 10 (-4) w/v aqueous solution of the copolymer, the strong hydrophobic attraction between the hydrophobized mica surfaces across water was replaced by strongly repulsive normal forces between them. These were attributed to the osmotic repulsion arising from the confined counterions at long-range, together with steric repulsion between the compressed brush layers at shorter range. The corresponding shear forces on sliding the surfaces were extremely low and below our detection limit (+/-20-30 nN), even when compressed down to a volume fraction close to unity. On further compression, very weak shear forces (130 +/- 30 nN) were measured due to the increase in the effective viscous drag experienced by the compressed, sliding layers. At separations corresponding to pressures of a few atmospheres, the shearing motion led to abrupt removal of most of the chains out of the gap, and the surfaces jumped into adhesive contact. The extremely low frictional forces between the charged brushes (prior to their removal) is attributed to the exceptional resistance to mutual interpenetration displayed by the compressed, counterion-swollen brushes, together with the fluidity of the hydration layers surrounding the charged, rubbing polymer segments.

Polyelectrolyte brushes were built on mica by anchoring polystyrene-poly(acrylic acid) (PS-b-PAA) diblock copolymers at a controlled surface density in a polystyrene monolayer covalently attached to OH-activated mica surfaces. Compared to physisorbed polymer brushes, these irreversibly attached charged brushes allow the polymer grafting density to remain constant upon changes in environmental conditions (e.g., pH, salt concentration, compression, and shear). The normal interaction and friction forces as a function of surface separation distance and at different concentrations of added salt (NaCl) were investigated using a surface forces apparatus. The interaction force profiles were completely reversible both on loading and receding and were purely repulsive. For a constant polymer grafting density, the influence of the polyelectrolyte charges and the Debye screening effect on the overall interaction forces was investigated. The experimental interaction force profiles agree very well with scaling models developed for neutral and charged polymer brushes. The variation of the friction force between two PAA brushes in motion with respect to each other as a function of surface separation distance appeared to be similar to that observed with neutral brushes. This similarity suggests that the increase in friction is associated with an increase in mutual interpenetration upon compression as observed with neutral polymers. The effect of the PAA charges and added ions was more significant on the repulsive normal forces than on the friction forces. The reversible characteristics of the normal force profiles and friction measurements confirmed the strong attachment of the PAA brushes to the mica substrate. High friction coefficients (ca 0.3) were measured at relatively high pressures (40 atm) with no surface damage or polymer removal.

Mica substrates were activated by a plasma method leading to OH-functionalized surfaces to which an atom transfer radical polymerization (ATRP) radical initiator was covalently bound using standard siloxane protocols. The unprecedented covalently immobilized initiator underwent radical polymerization with tert-butyl acrylate, yielding for the first time end-grafted polymer brushes that are covalently linked to mica. The initiator grafting on the mica substrate was confirmed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), while the change in the water contact angle of the OH-activated mica surface was used to follow the change in surface coverage of the initiator on the surface. The polymer brush and initiator film thicknesses relative to the virgin mica were confirmed by atomic force microscopy (AFM). This was done by comparing the atomic step-height difference between a protected area of freshly cleaved mica and a zone exposed to plasma activation, initiator immobilization, and then ATRP.

Dissipative particle dynamics (DPD) was used to investigate the behavior of two opposing end-grafted charged polymer brushes in aqueous media under normal compression and lateral shear. The effect of polymer molecular weight, degree of ionization, grafting density, ionic strength, and compression on the polymer conformation and the resulting shear force between the opposing polymer layers were investigated. The simulations were carried out for the poly(tert-butyl methacrylate)-block-poly(sodium sulfonate glycidyl methacrylate) copolymer, referred as PtBMA-b-PGMAS, end-attached to a hydrophobic surface for comparison with previous experimental data. Mutual interpenetration of the opposing end-grafted chains upon compression is negligible for highly charged polymer brushes for compression ratios ranging from 2.5 to 0.25. Under electrostatic screening effects or for weakly charged polymer brushes, a significant mutual interpenetration was measured. The variation of interpenetration thickness with separation distance, grafting density, and polymer size follows the same scaling law as the one observed for two opposing grafted neutral brushes in good solvent. However, compression between two opposing charged brushes results in less interpenetration relative to neutral brushes when considering equivalent grafting density and molecular weight. The friction coefficient between two opposing polymer-coated surfaces sliding past each other is shown to be directly correlated with the interpenetration thickness and more specifically to the number of polymer segments within the interpenetration layer.

Recent studies have revealed that, in contrast to non-associating liquids such as oils or organic solvents, salt-free water retains a viscosity close to its bulk value even when confined to films thinner than some 3 nm, indeed down to only one or two monolayers thick [1,2]. For the case of high concentration aqueous salt solution compressed down to subnanometer films between charged surfaces, the trapped hydrated ions serve to act as molecular ball-bearings, sustaining a large load while remaining very fluid under shear [3]. This behaviour is attributed to the tenacity of the hydration sheaths together with their rapid relaxation time. Finally, a very recent study [4] has shown that when charged polymer brushes in aqueous media are compressed and slid past each other, they provide a lubrication that is considerably superior to that afforded by neutral brushes: This is attributed on the one hand to the resistance to mutual interpenetration of the chains due to entropic barriers in the good-solvent conditions, and, on the other hand, to the hydration-sheaths on the charged polymer segments which can act – as noted above – as molecular ball-bearings.

Long-ranged forces between surfaces in a liquid control effects from colloid stability to biolubrication, and can be modified either by steric factors due to flexible polymers, or by surface charge effects. In particular, neutral polymer 'brushes' may lead to a massive reduction in sliding friction between the surfaces to which they are attached, whereas hydrated ions can act as extremely efficient lubricants between sliding charged surfaces. Here we show that brushes of charged polymers (polyelectrolytes) attached to surfaces rubbing across an aqueous medium result in superior lubrication compared to other polymeric surfactants. Effective friction coefficients with polyelectrolyte brushes in water are lower than about 0.0006-0.001 even at low sliding velocities and at pressures of up to several atmospheres (typical of those in living systems). We attribute this to the exceptional resistance to mutual interpenetration displayed by the compressed, counterion-swollen brushes, together with the fluidity of the hydration layers surrounding the charged, rubbing polymer segments. Our findings may have implications for biolubrication effects, which are important in the design of lubricated surfaces in artificial implants, and in understanding frictional processes in biological systems.

Recent Surface Forces Apparatus (SFA) experiments have shed new light on the roles of surface roughness and surface deformations, both at the molecular and microscopic scales, in determining adhesion and friction. Depending on the roughness, but also on other factors such as the stiffness and viscoelasticity of surfaces, these effects can cause the effective adhesion force to be orders of magnitude lower or higher than the thermodynamic (equilibrium) value, which in turn determines the frictional behaviour. The interactions of ‘ideal’, i.e., molecularly smooth, undamaged, surfaces are now quite well understood, both theoretically and experimentally. However, this is not the case for rough surfaces, which are difficult to define and characterize, and for which rigorous theories and reliable experimental data are lacking. Yet, most real or ‘engineering’ surfaces are rough on the nanometer to micrometer scale. This significantly affects their short-range interactions, their tribological behavior (adhesion, friction and lubrication) and their failure mechanisms (fracture and wear). Even when great care is taken to ensure smoothness, it is generally very difficult to produce a surface with a roughness of less than 25 A except over small areas (usually for research purposes) and it is known that even a few nm of roughness can reduce the adhesion force between hard surfaces by more than an order of magnitude, and totally change their tribological behavior. To date there is no general theory for the interactions of rough surfaces nor any systematic experiments that identify the main trends; for example, how does the adhesion force or friction coefficient of a particular surface depend on its roughness? Indeed, one of the major problems is that roughness itself is not well defined. Simply quoting the RMS roughness of a surface is too simplistic, whereas describing it rigorously in terms of its Fourier components is too impractical. This whole issue has recently come to be appreciated as central to many tribological questions. We have recently performed measurements, using the SFA and scanning lateral probe techniques, on various surfaces having different roughness in an attempt to uncover some general trends and principles that describe the dependence of adhesion, friction and wear on roughness. We find, for example, that there is a generic, approximately exponential, relationship for the repulsive force between two rough surfaces, and that for non-adhering surfaces the friction force is proportional to the load (not the real contact area) at the molecular level. These and other, such as the dynamic, aspects of the tribological interactions between rough surfaces are described and discussed.

In this study, micellar associations of cetyltrimethylammonium chloride/hydroxide with different Cl/OH exchange ratios and new surfactants having crown-ethers groups as their polar head were used to prepare mesoporous materials of M41S family, with subsequent calcination or CO 2 supercritical fluid extraction to remove the template. The influences of Cl/OH ratio, the size of the crown-ethers on the final phase and pore size were also investigated. The latter new templates were characterized by 1 H NMR and mass spectroscopy and the mesoporous materials by XRD, nitrogen physisorption and solid state 29 Si NMR spectroscopy.