A. Levent Demirel

From Static to Kinetic Friction in Confined Liquid Films

The transition from rest to sliding contact of atomically smooth solids separated by molecularly thin liquid films was studied. The films could be deformed nearly reversibly to a large fraction of the film thickness. The modulus of elasticity and yield stress were low, considerably less than for a molecular crystal or glass in the bulk. The transition to dissipative sliding was typically (but not always) discontinuous. The dissipative stress was then nearly velocity-independent. The similar response of monolayers strongly attached to the solid surfaces, presenting a well-defined interface for sliding, suggests that the physical mechanism of sliding may involve wall slip.

STICK TO SLIP TRANSITION AND ADHESION OF LUBRICATED SURFACES IN MOVING CONTACT

The friction of dry self‐assembled monolayers, chemically attached to a solid surface and comprising a well‐defined interface for sliding, is compared to the case of two solids separated by an ultrathin confined liquid. The monolayers were condensed octadecyltriethoxysilane (OTE). The liquid was squalane (C30H62), a film 2.0 nm thick confined between parallel plates of mica. The method of measurement was a surface forces apparatus, modified for oscillatory shear. The principal observations were the same in both cases: (1) Predominantly elastic behavior in the linear response state was followed by a discontinuous transition to a mostly dissipative state at larger deformations. The elastic energy stored at the transition was low, of the order of 0.1 kT per molecule. This transition was exactly repeatable in repetitive cycles of oscillation and reversible with pronounced hysteresis. (2) The dissipative stress in the sliding state was almost independent of peak sliding velocity when this was changed over several decades. Significant (although smaller) elastic stress also persisted, which decreased with increasing deflection amplitude but was almost independent of oscillation frequency. (3) The adhesive energy in the sliding state was significantly reduced from that measured at rest. This similarity of friction in the two systems, dry and wet sliding, leads us to speculate that, similar to plastic deformation of solids, sliding in the confined liquid films is the result of slippage along an interface.

Transition from static to kinetic friction in a model lubricated system

Molecularly thin confined fluids were deformed in shear faster than structural relaxations in response to shear could be accomplished, such that with increasing deformation the systems passed from the rest state to sliding. The response of these systems—two atomically smooth mica sheets separated by a fluid comprised of globularly shaped molecules [octamethylcyclotetrasiloxane]—was studied as a function of film thickness of the fluid (from 80 to 10 A, i.e, from ∼8 to ∼1 molecular dimensions), as a function of normal pressure, and as a function of deformation rate, using a modified surface forces apparatus. Whereas the linear response was always liquid-like provided that the deformation rate was sufficiently slow, a “stick-slip” transition from the rest state to sliding was observed when the deformation rate was large, provided that the oscillatory frequency sufficiently exceeded the inverse intrinsic relaxation time of the confined fluid. This transition was monotonic and reversible without hysteresis for...

Origins of solidification when a simple molecular fluid is confined between two plates

A simple globular-shaped liquid (octamethylcyclotetrasiloxane, OMCTS) was placed between two rigid mica plates at variable spacings comparable to the size of this molecule and the linear shear viscoelasticity of the confined interfacial film was measured. Strong monotonic increase of the shear relaxation time, elastic modulus, and effective viscosity were observed as the spacing was decreased below about 10 molecular dimensions. The frequency dependence of the viscoelastic spectra measured at different film thicknesses appeared to scale with reduced variables. The data are inconsistent with the abrupt first-order transition, from bulk fluid to solid with decreasing film thickness, whose possibility has been hypothesized, and suggest a glasslike transition instead.

Thermally curable fluorinated main chain benzoxazine polyethers via Ullmann coupling

Fluorinated main chain benzoxazine polyethers were prepared by Ullmann coupling of fluorinated benzoxazines in the presence of a nano-copperoxide catalyst. Various parameters such as the monomer structure, temperature, and the effect of catalyst on the polymerization were studied. The benzoxazine groups present in the polyether structure were shown to readily undergo thermally activated ring-opening polymerization in the absence of an added catalyst forming cross-linked networks. The thermal stability of the cured polymers was investigated and compared to that of classical polybenzoxazines. The lower surface energy of the fluorinated polymers made ultrathin films (∼20 nm thick) stable against dewetting at curing temperatures and resulted in thermally cured smooth coatings on solid substrates.

Effect of structural isomerism and polymer end group on the pH-stability of hydrogen-bonded multilayers.

Association of tannic acid (TA) with structurally isomeric poly(N-isopropylacrylamide) (PNIPAM) and poly(2-isopropyl-2-oxazoline) (PIPOX) has been examined at surfaces to understand the effect of different molecular arrangements in a polymer repeating unit of structural isomers on the construction and pH-stability of hydrogen-bonded multilayers. Films were fabricated using layer-by-layer (LbL) technique through hydrogen-bonding interactions primarily between carbonyl groups of neutral polymers and hydroxyl groups of TA molecules at pH 2. PIPOX and TA formed thinner and more stable films in the pH scale with a critical dissolution pH of 9 when compared to films of PNIPAM and TA with a critical pH of 8. The differences in the thickness and pH-stability were due to different conformational behavior of PNIPAM and PIPOX in water which affects the accessibility of carbonyl groups for participation in the hydrogen bonding and the number of binding sites between the polymer pairs. Addition of electrostatic interactions by introducing amino groups only at the PIPOX chain end shifted the critical dissolution pH to higher values and resulted in gradual dissolution of the films in a wide pH range of 9-12. Such films hold promise for use in biomedical field due to biocompatibility and lower critical solution temperature (LCST) behavior at near physiological temperature of PNIPAM and PIPOX together with the pH-response of the hydrogen-bonded films.

Self-assembled poly(2-ethyl-2-oxazoline) fibers in aqueous solutions

Poly(2-ethyl-2-oxazoline) (PEOX) formed self-assembled fibers in aqueous solutions above the cloud point temperature (Tc) through a slow crystallization process. The fiber formation above Tc happened both in pure water and in the presence of salting-in (SCN−) and salting-out (CH3COO−) ions. The crystal structure and the melting temperature of the PEOX fibers were determined.

Polystyrene/octadecyltrichlorosilane superhydrophobic coatings with hierarchical morphology

A simple, one pot dip-coating process for the fabrication of superhydrophobic coatings using polystyrene (PS) and octadecyltrichlorosilane (OTS) is introduced. The hierarchical coating morphology and the resulting surface wettability were controlled by OTS concentration and by the number of dipping cycles. The coatings showed good durability for applications.

Effect of anions on the cloud point temperature of aqueous poly(2-ethyl-2-oxazoline) solutions.

Poly(2-alkyl-2-oxazoline)s have recently gained attention in especially biological applications due to their lower critical solution temperature being close to the body temperature and their biocompatibility. The understanding of how cloud point temperature (T(c)) depends on the salt concentration and the molecular mechanisms responsible for such behavior are important to tune T(c) as desired by the applications. In this paper, we report the effect of a series of sodium salts on T(c) of aqueous poly(2-ethyl-2-oxazoline) (PEOX) solutions by dynamic light scattering. PEOX samples having four different molecular weights were investigated, and the results were compared with those of poly(N-isopropylacrylamide) (PNIPAM), the mostly investigated and used thermoresponsive polymer. Kosmotropic anions decreased T(c) linearly while chaotropic anions increased T(c) nonlinearly with salt concentration. The contributions of different mechanisms to T(c) change have been discussed. Our results indicate that the dominant mechanism is the dehydration of PEOX for divalent kosmotropic anions (CO(3)(2-), SO(4)(2-), S(2)O(3)(2-)) and direct binding for chaotropic anions (NO(3)(-), I(-), ClO(4)(-), SCN(-)). For the remaining monovalent kosmotropic anions (H(2)PO(4)(-), F(-), Cl(-), Br(-)), a combination of dehydration and surface tension mechanisms was in effect. The additional contribution of the surface tension mechanism for the monovalent kosmotropic anions was inferred for different molecular weight PEOX samples and also for PNIPAM. With PEOX molecular weight decreasing from 500,000 to 5000 g/mol, T(c) decreased less with salt concentration which was attributed to the contribution of the surface tension mechanism. For PEOX samples, the decrease of T(c) with kosmotropic anion concentration was faster compared to PNIPAM due to differences in their chemical structure. Our results show that the molecular mechanisms of interactions between PEOX chains and specific anions can simply be inferred from determination of T(c) by a common technique-dynamic light scattering.

Motion of Single Terrylene Molecules in Confined Channels of Poly(butadiene)-Poly(ethylene oxide) Diblock Copolymer

The motion of terrylene probe molecules in confined PB channels of an asymmetric PB-PEO diblock copolymer has been investigated by single molecule tracking. The one-dimensional diffusion coefficients were found to be significantly smaller and had a narrower distribution compared to two-dimensional diffusion coefficients in PB. The trajectories of some single molecules showed unusual behavior of directed motion where mean square displacement had a parabolic dependence on lag time. The likely origin of this behavior is discussed in terms of local variations in the PB channel width and the resulting change in the local density. The results show the effect of nonuniformities and heterogeneities in the channels on the motion of single molecules and demonstrate the sensitivity of single molecule tracking in characterizing self-assembled block copolymer morphologies.