Publications

Lipid bilayers, ubiquitous in living systems, form lubricious boundary layers in aqueous media, with broad relevance for biolubrication, especially in mechanically stressed environments such as articular cartilage in joints, as well as for modifying material interfacial properties. Model studies have revealed efficient lubricity by single-component lipid bilayers; synovial joints, however (e.g. hips and knees), comprise over a hundred different lipids, raising the question of whether this is natural redundancy or whether it confers any lubrication benefits. Here, we examine lubrication by progressively more complex mixtures of lipids representative of those in joints, using a surface forces balance at physiologically relevant salt concentrations and pressures. We find that different combinations of such lipids differ very significantly in the robustness of the bilayers to hemifusion under physiological loads (when lubrication breaks down), indicating a clear lubrication synergy afforded by multiple lipid types in the bilayers. Insight into the origins of this synergy is provided by detailed molecular dynamics simulations of potential profiles for the formation of stalks, the essential precursors of hemifusion, between bilayers of the different lipid mixtures used in the experiments. These reveal how bilayer hemifusionand thus lubrication breakdowndepends on the detailed lipid bilayer composition, through the corresponding separation into domains that are better able to resist stalk formation. Our results shed light on the role of lipid-type proliferation in biolubrication synergy, point to improved treatment modalities for common joint diseases such as osteoarthritis, and indicate how lipid-based interfacial modification in a materials context may be optimized.

Transient electric fields across cell bilayer membranes can lead to electroporation and cell fusion, effects crucial to cell viability whose biological implications have been extensively studied. However, little is known about these behaviours in a materials context. Here we find that transmembrane electric fields can lead to a massive, reversible modulation of the sliding friction between surfaces coated with lipid-bilayer membranesa 200-fold variation, up to two orders of magnitude greater than that achieved to date. Atomistic simulations reveal that the transverse fields, resembling those at cell membranes, lead to fully reversible electroporation of the confined bilayers and the formation of inter-bilayer bridges analogous to the stalks preceding intermembrane fusion. These increase the interfacial dissipation through reduced hydration at the slip plane, forcing it to revert in part from the low-dissipation, hydrated lipidheadgroup plane to the intra-bilayer, high-dissipation acyl tail interface. Our results demonstrate that lipid bilayers under transmembrane electric fields can have striking materials modification properties.

Hydrogels with pure hydrophilic network have received much attention due to their excellent low frictional behavior. However, the lubrication performance of hydrogels is not satisfied under high-speed condition due to the energy dissipation caused by adsorbed polymer chains as well as the failure of lubricating mechanisms accompanied by the transition of lubrication regime. In this work, interpenetrating double-network organohydrogels were constructed by combining hydrophilic and oleophilic polymer networks to modify the physiochemical properties of surface polymer chains, especially the chain mobility. The oleophilic polymer network spatially restricting the mobility of the swollen hydrophilic network in water, resulted in a low coefficient of friction (ca. 0.01) compared with conventional hydrogels at high speed (0.1ms−1). Meanwhile, the organohydrogels had superior wear resistance, with almost no wear observed on the sliding track after 5kcycles of rubbing at high speed. The design concept of organohydrogels can be extended to a variety of low-wear, highly-lubricating materials.

Transient electric fields across cell bilayer membranes can lead to electroporation, as well as to cell fusion, and have been extensively studied. We find that transmembrane electric fields similar to those in cells can lead to a massive, reversible modulation--by up to 200-fold--of the interfacial energy dissipation between surfaces sliding across the lipid bilayer membranes. Atomistic simulations reveal that this arises from (fully reversible) electroporation of the interfacially-confined bilayers, and formation of bilayer bridges analogous to stalks preceding intermembrane fusion. These cell-membrane-mimicking effects topologically-force the slip to partially-revert from the low-dissipation, hydrated lipid-headgroups plane to the intra-bilayer, high-dissipation acyl tail interface. Our results demonstrate that lipid bilayers under transmembrane electric fields can have striking materials-modification properties, and shed new light on membrane hemifusion.

Drug delivery via nanovehicles is successfully employed in several clinical settings, yet bacterial infections, forming microbial communities in the form of biofilms, present a strong challenge to therapeutic treatment due to resistance to conventional antimicrobial therapies. Liposomes can provide a versatile drug-vector strategy for biofilm treatment, but are limited by the need to balance colloidal stability with biofilm penetration. We have discovered a liposomic functionalization strategy, using membrane-embedded moieties of poly[2-(methacryloyloxy)ethyl phosphorylcholine], pMPC, that overcomes this limitation. Such pMPCylation results in liposomic stability equivalent to current functionalization strategies (mostly PEGylation, the present gold-standard), but with strikingly improved cellular uptake and cargo conveyance. Fluorimetry, cryo-electron, and fluorescence microscopies reveal a far-enhanced antibiotic delivery to model Pseudomonas aeruginosa biofilms by pMPC-liposomes, followed by faster cytosolic cargo release, resulting in significantly greater biofilm eradication than either PEGylation or free drug. Moreover, this combination of techniques uncovers the molecular mechanism underlying the enhanced interaction with bacteria, indicating it arises from bridging by divalent ions of the zwitterionic groups on the pMPC moieties to the negatively charged lipopolysaccharide chains emanating from the bacterial membranes. Our results point to pMPCylation as a transformative strategy for liposomal functionalization, leading to next-generation delivery systems for biofilm treatment.

The hydration layer surrounding the phosphocholine headgroups of single-component phosphatidylcholine lipids, or of lipid-mixtures, assembled at an interface greatly modifies the interfacial properties and interactions. As water molecules within the hydration layer are held tightly by the headgroup but are nonetheless very fluid on shear, the boundary lipid layers, exposing the highly hydrated headgroup arrays, can provide efficient boundary lubrication when sliding against an opposing surface, at physiologically high contact pressures. In addition, any free lipids in the surrounding liquid can heal defects which may form during sliding on the boundary phosphatidylcholine layer. Similar boundary lipid layers contribute to the lubricating, pressure-bearing, and wear-protection functions of healthy articular joints. This review presents a survey of the relationship between the molecular composition of the interfacial complex and the lubrication behavior of the lipid-based boundary layers, which could be beneficial for designing boundary lubricants for intra-articular injection for the treatment of early osteoarthritis.

The viscoelectric effect concerns the increase in viscosity of a polar liquid in an electric field due to its interaction with the dipolar molecules, and was first determined for polar organic liquids more than 80 years ago. For the case of water, however, the most common polar liquid, direct measurement of the viscoelectric effect is challenging and has not to date been carried out, despite its importance in a wide range of electrokinetic and flow effects. In consequence, estimates of its magnitude for water vary by more than 3 orders of magnitude. Here we measure the viscoelectric effect in water directly using a sur-face force balance (SFB), by measuring the dynamic approach of two molecularly-smooth surfaces with a controlled, uniform electric field between them across highly-purified water. As the water is squeezed out of the gap between the approaching surfaces, viscous damping dominates the approach dynamics; this is modulated by the viscoelectric effect under the uniform transverse electric field across the water, enabling its magnitude to be directly determined as a function of the field. We find a value for this mag-nitude which differs respectively by 1 and by 2 orders of magnitude from its highest and lowest previ-ously estimated values.

Healthy articular cartilage, covering the ends of bones in major joints such as hips and knees, presents the most efficiently-lubricated surface known in nature, with friction coefficients as low as 0.001 up to physiologically high pressures. Such low friction is indeed essential for its well-being. It minimizes wear-and-tear and hence the cartilage degradation associated with osteoarthritis, the most common joint disease, and, by reducing shear stress on the mechanotransductive, cartilage-embedded chondrocytes (the only cell type in the cartilage), it regulates their function to maintain homeostasis. Understanding the origins of such low friction of the articular cartilage, therefore, is of major importance in order to alleviate disease symptoms, and slow or even reverse its breakdown. This progress report considers the relation between frictional behavior and the cellular mechanical environment in the cartilage, then reviews the mechanism of lubrication in the joints, in particular focusing on boundary lubrication. Following recent advances based on hydration lubrication, a proposed synergy between different molecular components of the synovial joints, acting together in enabling the low friction, has been proposed. Additionally, recent development of natural and bio-inspired lubricants is reviewed.

Duncan Dowson, whom this issue commemorates, was a world leader in the field of biotribology, with prolific contributions both in fluid-based and boundary lubrication of biological tissues, in particular articular cartilage, a central issue in biotribology due to its importance for joint homeostasis. Here we explore further the issue of cartilage boundary lubrication, which has been attributed to phospholipid (PL)-exposing layers at the cartilage surface in part. A surface force balance (SFB) with unique sensitivity is used to investigate the normal and frictional interactions of the boundary layers formed by PLs extracted from osteoarthritic (OA) human synovial fluid (hSF). Our results reveal that vesicles of the OA-hSF lipids rupture spontaneously to form bilayers on the mica substrate (which, like the in-vivo articular cartilage surface in synovial joints, is negatively-charged) which then undergo hemifusion at quite low pressures in the SFB, attributed to the large heterogeneity of the hSF lipids. Nanometric friction measurements reveal friction coefficients μ ≈ 0.03 across the hemifused bilayer of these lipids, indicating residual hydration lubrication at the lipid-headgroup/substrate interface. Addition of calcium ions causes an increase in friction to μ ≈ 0.2, attributed either to calcium-bridging attraction of lipid headgroups to the negatively-charged substrate, or a shift of the slip plane to the more dissipative hydrophobic-tail/hydrophobic-tail interface. Our results suggest that the heterogeneity and composition of the OA-hSF lipids may be associated with higher friction at the cartilage boundary layers and thus a connection with greater wear and degradation due to hemifusion of the exposed lipid bilayers.

Osteoarthritic joints contain lower molecular weight (MW) hyaluronan (hyaluronic acid, HA) than healthy joints. To understand the relevance of this HA-size effect for joint lubrication, the friction and surface structure of cartilage-emulating surfaces with HA of different MW were studied using a surface force balance (SFB), and atomic force microscopy (AFM) . Gelatin (gel)-covered mica surfaces were coated with either high MW HA (HHA), medium MW HA (MHA) or low MW HA (LHA), and lipids of Hydrogenated Soy L-α-phosphatidylcholine (HSPC) in the form of small unilamellar vesicles, using a layer-by-layer assembly method. SFB results indicate that the gel-HHA-HSPC boundary layer provides very efficient lubrication, attributed to hydration lubrication at the phosphocholine head-groups exposed by the HA-attached lipids, with friction coefficients (COF) as low as l0-310-4 at contact stresses at least up to P = 120 atm. However, for the gel-MHA-HSPC and gel-LHA-HSPC surfaces, the friction, initially low, increases sharply at much lower pressures (up to 3060 atm at most). This higher friction with the shorter chains may be due to their weaker total adhesion energy to the gelatin, where the attraction between the negatively-charged HA and the weakly-positively charged gelatin is attributed largely to counterion-release entropy. Thus the complexes of LHA and MHA with the lubricating HSPC lipids are more easily removed by shear during sliding, especially at high stresses, than is the HHA-HSPC complex which is strongly adhered to the gelatin. This is ultimately the reason for lower-pressure lubrication breakdown with the shorter polysaccharides. Our results provide molecular level insight into why the decrease in HA molecular weight in osteoarthritic joints may be associated with higher friction at the articular cartilage surface, and may have relevance for treatments of osteoarthritis involving intra-articular HA injections.

Hydration lubrication has emerged as a new paradigm for lubrication in aqueous and biological media, accounting especially for the extremely low friction (friction coefficients down to 0.001) of articular cartilage lubrication in joints. Among the ensemble of molecules acting in the joint, phosphatidylcholine (PC) lipids have been proposed as the key molecules forming, in a complex with other molecules including hyaluronic acid (HA), a robust layer on the outer surface of the cartilage. HA, ubiquitous in synovial joints, is not in itself a good boundary lubricant, but binds the PC lipids at the cartilage surface; these, in turn, massively reduce the friction via hydration lubrication at their exposed, highly hydrated phosphocholine headgroups. An important unresolved issue in this scenario is why the free HA molecules in the synovial fluid do not suppress the lubricity by adsorbing simultaneously to the opposing lipid layers, i.e., forming an adhesive, dissipative bridge between them, as they slide past each other during joint articulation. To address this question, we directly examined the friction between two hydrogenated soy PC (HSPC) lipid layers (in the form of liposomes) immersed in HA solution or two palmitoyl-oleoyl PC (POPC) lipid layers across HA-POPC solution using a surface force balance (SFB). The results show, clearly and surprisingly, that HA addition does not affect the outstanding lubrication provided by the PC lipid layers. A possible mechanism indicated by our data that may account for this is that multiple lipid layers form on each cartilage surface, so that the slip plane may move from the midplane between the opposing surfaces, which is bridged by the HA, to an HA-free interface within a multilayer, where hydration lubrication is freely active. Another possibility suggested by our model experiments is that lipids in synovial fluid may complex with HA, thereby inhibiting the HA molecules from adhering to the lipids on the cartilage surfaces.

Hydration layers surrounding charges or zwitterionic moieties have long been known to play important roles in areas including antifouling and colloidal stability, and particularly over the past 15 years or so, their role in boundary lubrication has been widely investigated. Hydration repulsion because of hydrated ions or polar groups present on surfaces may dominate their interactions at high electrolyte concentrations, so that Derjaguin-Landau-Verwey-Overbeek theory does not apply. Hydration shells, strongly held by the charges they surround, can sustain large pressures without being squeezed out, while by rapidly relaxing, and they behave like a fluid during shear; this may lead to their acting as lubrication vectors with outstanding friction reduction properties. This review considers hydration layers around trapped ions, polymer brushes, and amphiphiles (surfactants and phosphatidylcholines), focusing on their lubrication properties. Finally, we suggest some prospects for further development of current hydrated vectors and designing new hydrated vectors for modifying surface interactions.

A wide range of phosphatidylcholine (PC)
lipids with different degrees of unsaturation has been
identified in the human synovial fluid and on the cartilage
surface. The outstanding lubricity of the articular cartilage
surface has been attributed to boundary layers comprising
complexes of such lipids, though to date, only lubrication by
single-component PC-lipid-based boundary layers has been
investigated. As distinguishable lubrication behavior has been
found to be related to the PC structures, we herein examined
the surface morphology (on mica) and the lubrication ability
of binary PC lipid mixtures, 1,2-dipalmitoyl-sn-glycero-3-
phosphocholine (DPPC) and 1-palmitoyl-2-oleoyl-sn-glycero3-phosphocholine (POPC), using atomic force microscopy (AFM) and a surface force balance (SFB). These two PC lipids are
among the most abundant saturated and unsaturated PC components in synovial joints. Small unilamellar vesicles (SUVs)
prepared from DPPC-POPC mixtures (8:2, 5:5, and 2:8, molar ratios) ruptured and formed bilayers on mica. The normal and
shear forces between two DPPC-POPC bilayer-coated mica surfaces across the corresponding SUV dispersions show good
boundary lubrication (friction coefficients ≤ ca. 10−4
) up to contact stresses of 8.3 ± 2.2 MPa for 8:2 DPPC-POPC and 5.0 ±
1.7 MPa for the others. Hemifusion induced at high normal pressures was observed, probably because of the height mismatch of
two components. Reproducible successive approaches after hemifusion indicate rapid self-healing of the mica-supported bilayers
in the presence of the SUVs reservoir. This work is a first step to provide insight concerning the lubrication, wear, and healing of
the PC-based boundary layers, which must consist of multicomponent lipid mixtures, on the articular cartilage surface.

We have prepared phosphatidylcholine (PC) vesicles (liposomes) incorporating a novel lipid/poly-phosphocholine conjugate. This both stabilizes the liposomes against aggregation (for example, during storage or when being delivered) and allows them to act as very efficient lubricating elements readily attaining superlubric performance (defined as coefficient of friction mu

Using viscosity and dynamic light scattering (DLS) measurements, we monitored the changes in the properties of dispersions of chitosan (a cationic polysaccharide) in acidic solution over a period of up to 700 h. Different polymer concentrations, weight average molecular weights, and degrees of deacetylation were examined. We found that the solution rheology and chitosan aggregates continue to change even up to 700 h. It was observed, remarkably, using both capillary and cone and plate viscometry that the viscosity decreased significantly during the storage period of the chitosan dispersions, with a rapid initial decrease and a slow approach to the steady state value. DLS measurements over this period could be interpreted in terms of a gradual decrease in the size of the chitosan aggregates in the dispersion. This behavior is puzzling, insofar as one expects the dissolution of compact polymer aggregates with time into individual polymer chains to increase the viscosity rather than decrease it as observed: We attribute this apparently anomalous behavior to the fact that the chitosan aggregates are rigid crystalline rod-like entities, which dissolved with time from dispersion of overlapping rods (with high viscosity) into solution of individual random coils (with lower viscosity). A detailed model comparing the hydrodynamic behavior of the initial overlapping rod-like aggregates with the subsequent free coils in solution is in semi-quantitative agreement with our observation. Published by AIP Publishing.

Poly[2-(methacryloyloxy)ethylphosphorylcholine] (pMPC) brushes provide extremely low friction coefficients up to high compressions, but their use as boundary lubricating layers is limited by the challenge of surface grafting of the chains. Coating by thin layers of cross-linked pMPC hydrogels may provide an attractive alternative. Here we use a surface force balance (SFB) and other techniques to examine the effect of light cross-linking (0.1% cross-linker) on the surface interactions and frictional behavior of grafted-from pMPC brushes on mica, up to physiologically high contact pressures. Atomic force microscopy, X-ray photoelectron spectroscopy, and interferometric surface-excess measurements show little difference between the non-cross-linked (linear) pMPC brushes and the cross-linked brushes prepared under otherwise identical conditions. Normal force-distance profiles between the polymer-bearing surfaces, however, reveal a marked compaction of the unperturbed thickness of the cross-linked brushes relative to linear ones, attributed to the cross-linking which limits chain swelling. The cross-linked pMPC layers exhibit very low friction (friction coefficients of order 10^-3-10^-4, depending on sliding velocities), similar to the corresponding linear brushes and due to hydration lubrication by the highly hydrated phosphocholine monomer structure. Within the range of our parameters, however, there is a marked qualitative difference in the dependence of friction on sliding velocity v_s. While for the linear brushes friction is only very weakly v_s-dependent (over 3 orders of magnitude in v_s), due to a self-regulating brush interpenetration, for the cross-linked brushes friction increases markedly with v_s (∼v_s^1/2), an effect attributed to suppression of interpenetration by the cross-links.

The lubrication properties of saturated PC lipid vesicles containing high cholesterol content under high loads were examined by detailed surface force balance measurements of normal and shear forces between two surface-attached lipid layers. Forces between two opposing mica surfaces bearing distearoylphosphatidylcholine (PC) (DSPC) small unilamellar vesicles (SUVs, or liposomes), or bilayers, with varying cholesterol content were measured across water, whereas dimyristoyl PC (DMPC), dipalmitoyl PC (DPPC), and DSPC SUVs containing 40% cholesterol were measured across liposome dispersions of SUVs of the same lipid composition as in the adsorbed layers. The results clearly demonstrate decreased stability and resistance to normal load with the increase in cholesterol content of DSPC SUVs. Friction coefficients between two 10% cholesterol PC-bilayers were in the same range as for 40% cholesterol bilayers (μ ≈ 10^-3), indicating that cholesterol has a more substantial effect on the mechanical properties of a bilayer than on its lubrication performance. We further find that the lubrication efficiency of DMPC and DPPC with 40% cholesterol is superior to that of DSPC 40% cholesterol, most likely because of enhanced hydration-lubrication in these systems. We previously found that when experiments are performed in the presence of a lipid reservoir, layers can self-heal and therefore their robustness is less important under such conditions. We conclude that the effect of cholesterol in decreasing the stability is more pronounced than its effect on hydration, but the stability is, in turn, less important when a lipid reservoir is present. This study complements our previous work and sheds light on the effect of cholesterol, a prominent and important physiological lipid, on the mechanical and lubrication properties of gel-phase lipid layers.

Extending earlier studies where phosphocholinated brushes and phosphocholineexposing phosphatidylcholine lipid bilayer vesicles (PCliposomes) were shown to be very efficient boundary lubricants in aqueous media by virtue of the highlyhydrated phophocholine groups, we examined interactions between surfaces bearing phosphocholinated polystyrene nanoparticles (pcPSNPs). We synthesized such particles by incorporation of alkyl chains terminated with phosphocholine groups in the PSNP, with the hydrophilic phosphocholines exposed at the NP surface. These were then allowed to adsorb onto mica surfaces, and the normal and shear interactions between them were examined in a surface force balance. On moderate compressions (contact pressures>9atm) the pcPSNPs were squeezed out, leaving a single layer between the surfaces. Shear of the surfaces revealed a large frictional dissipation, with a friction coefficient μ≈0.2, in contrast to our expectations that such phosphocholinated NPs would provide highly lubricating analogues of PCliposomes (for which μ≈10−3 10−4). This is attributed to a number of factors, including the inherent roughness of the NP multilayers at low compressions and the relatively low areal density of the phosphocholine groups on the PSNP surfaces. In particular, at higher compressions, sliding results in energydissipating breaking and reforming of phosphocholine/mica (dipole/charge) bonds at the mica surfaces (and thus high friction), because of bridging of the surfaces by a single layer of pcPSNPs.

Highly efficient lubricating boundary layers at biosurfaces such as cartilage have been proposed to comprise phospholipids complexed with biomacromolecules exposed at the surfaces. To gain insight into this, a systematic study on the normal and frictional forces between surfaces bearing a sequentially deposited model alginate-on-chitosan bilayer, bearing different adsorbed phosphatidylcholine (PC) liposomes, was carried out using a surface force balance. Structures of the resulting surface complexes were determined using atomic force microscopy (AFM) and cryo-scanning electron microscopy (cryo-SEM). The liposome/lipid-polymer complexes could maintain their integrity up to high pressures in terms of both normal and shear interactions between the surfaces, which were repeatable, reproducible, and revealed very low friction (coefficient of friction μ down to 10^-3-10^-4, depending on the PC used) up to pressures of hundreds of atm. We attribute this remarkable lubrication capability ultimately to hydration lubrication acting at the hydrated phosphocholine headgroups of the PC lipids, either exposed at the liposome surfaces or through complexation with the polyelectrolyte bilayer. Values of μ, while low, were roughly an order of magnitude higher than for the same PC vesicles adsorbed on bare mica, a difference attributed to their lower density on the bilayer; the bilayer, however, stabilized the PC-vesicles far better than bare mica against rupture and shear at high compressions and sliding.

Frictional energy dissipation between sliding solid surfaces in aqueous media may proceed by different pathways. Using a surface force balance (SFB), we have examined systematically how such dissipation is mediated by the series of hydrated cations M⁺ = Li⁺, Na⁺, and K⁺ that are trapped between two atomically smooth, negatively charged, mica surfaces sliding across the ionic solutions over many orders of magnitude loading. By working at local contact pressures up to ca. 30 MPa (∼300 atm), up to 2 orders of magnitude higher than earlier studies, we could show that the frictional dissipation at constant sliding velocity, represented by the coefficient of sliding friction ^^Petroleum Research Fund of the American Chemical Society _M+, decreased as μ_Li+ > μ_Na+ μ_K+. This result contrasts with the expectation (in conceptual analogy with the Hofmeister series) that the lubrication would improve with the extent of ionic hydration, since that would have led to the opposite μ_M+ sequence. It suggests, rather, that frictional forces, even in such simple systems, can be dominated by rate-activated pathways where the size of the hydration shell becomes a dissipative liability, rather than by the hydration-shell dissipation expected via the hydration lubrication mechanism.

Measurements of normal and shear (frictional) forces between mica surfaces across small unilamellar vesicle (SUV) dispersions of the phosphatidylcholine (PC) lipids DMPC (14 : 0), DPPC (16 : 0) and DSPC (18 : 0) and POPC (16 : 0, 18 : 1), at physiologically high pressures, are reported. We have previously studied the normal and shear forces between two opposing surfaces bearing PC vesicles across pure water and showed that liposome lubrication ability improved with increasing acyl chain length, and correlated strongly with the SUV structural integrity on the substrate surface (DSPC > DPPC > DMPC). In the current study, surprisingly, we discovered that this trend is reversed when the measurements are conducted in SUV dispersions, instead of pure water. In their corresponding SUV dispersion, DMPC SUVs ruptured and formed bilayers, which were able to provide reversible and reproducible lubrication with extremely low friction (μ -4) up to pressures of 70-90 atm. Similarly, POPC SUVs also formed bilayers which exhibited low friction (μ -4) up to pressures as high as 160 atm. DPPC and DSPC SUVs also provided good lubrication, but with slightly higher friction coefficients (μ = 10^-3-10^-4). We believe these differences originate from fast self-healing of the softer surface layers (which are in their liquid disordered phase, POPC, or close to it, DMPC), which renders the robustness of the DPPC or DSPC (both in their solid ordered phase) less important in these conditions. Under these circumstances, the enhanced hydration of the less densely packed POPC and DMPC surface layers is now believed to play an important role, and allows enhanced lubrication via the hydration lubrication mechanism. Our findings may have implications for the understanding of complex biological systems such us biolubrication of synovial joints.

Jee et al. assert (1) that the effect we measurewhat happens to a lubricant film thickness in individual slip events during intermittent stickslip sliding (2)was already measured long ago (3, 4), and with better resolution. We are bemused by this assertion because in the works cited (3, 4) not only is intermittent stickslip friction, with its characteristic saw-tooth pattern, not shown or measured, but their inability to measure what happens during the individual, fleeting slip eventsthe key finding of our own study (2)is explicitly stated in the papers themselves (below).

Intermittent sliding (stick-slip motion) between solids is commonplace (e.g., squeaking hinges), even in the presence of lubricants, and is believed to occur by shear-induced fluidization of the lubricant film (slip), followed by its resolidification (stick). Using a surface force balance, we measure how the thickness of molecularly thin, model lubricant films (octamethylcyclotetrasiloxane) varies in stick-slip sliding between atomically smooth surfaces during the fleeting (ca. 20 ms) individual slip events. Shear fluidization of a film of five to six molecular layers during an individual slip event should result in film dilation of 0.4-0.5 nm, but our results show that, within our resolution of ca. 0.1 nm, slip of the surfaces is not correlated with any dilation of the intersurface gap. This reveals that, unlike what is commonly supposed, slip does not occur by such shear melting, and indicates that other mechanisms, such as intralayer slip within the lubricant film, or at its interface with the confining surfaces, may be the dominant dissipation modes.

Why is friction in healthy hips and knees so low? Hydration lubrication, according to which hydration shells surrounding charges act as lubricating elements in boundary layers (including those coating cartilage in joints), has been invoked to account for the extremely low sliding friction between surfaces in aqueous media, but not well understood. Here we report the direct determination of energy dissipation within such sheared hydration shells. By trapping hydrated ions in a 0.4-1 nm gap between atomically smooth charged surfaces as they slide past each other, we are able to separate the dissipation modes of the friction and, in particular, identify the viscous losses in the subnanometre hydration shells. Our results shed light on the origins of hydration lubrication, with potential implications both for aqueous boundary lubricants and for biolubrication.

The lubrication properties of 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) extended supported bilayers were studied and compared to those of surface-attached DSPC small unilamellar vesicles (liposomes) in order to elucidate the effect of phospholipid geometrical packaging on the lubrication and mechanical properties of these boundary layers. The topography and response to the nanoindentation of bilayer-and liposome-covered surfaces were studied by an atomic force microscope (AFM). In parallel, normal and shear (frictional) forces between two opposing surfaces bearing DSPC vesicles/bilayers across water were studied with the surface force balance (SFB). A correlation between nanomechanical performance in the AFM and stability and lubrication in the SFB was observed. Bilayers were readily punctured by the AFM tip and exhibited substantial hysteresis between approach and retraction curves, whereas liposomes were not punctured and exhibited purely elastic behavior. At the same time, SFB measurements showed that bilayers are less stable and less efficient lubricants compared to liposomes. Bilayers provided efficient lubrication with very low friction coefficients, 0.002-0.008 up to pressures of more then 50 atm. However, bilayers were less robust and tended to detach from the surface as a result of shear, leading to high friction for subsequent approaches at the same contact position. In contrast, liposomes showed reversible and reproducible behavior under shear and compression, exhibiting ultralow friction coefficients of μ ≈10^-4 for pressures as high as 180 atm. This is attributed to the increased mechanical stability of the self-closed, closely packed liposomes, which we believe results from the more defect-free nature of the finitely sized vesicles.

Using a surface force balance (SFB), we measured the boundary friction and the normal forces between mica surfaces immersed in a series of alkyltrimethylammonium chloride (TAC) surfactant solutions well above the critical micelle concentration (CMC). The surfactants that were used-C ₁₄TAC, C₁₆TAC, and C₁₈TAC-varied by the length of the alkyl chain. The structures of the adsorbed layers on the mica were obtained using AFM imaging and ranged from flat bilayers to rodlike micelles. Despite the difference in alkyl chain, all the surfactant solutions reduce the friction between the two mica surfaces enormously relative to immersion in water, and have similar friction coefficients (μ -0.001). The pressure at which such lubrication breaks down is higher for the surfactants with longer chain lengths and indicates that an important role of the chain length is to provide a more robust structure of the adsorbed layers which maintains its integrity to higher pressures.

Using a surface force balance, we have measured the forces between bare (hydrophilic) mica surfaces, and between hydrophobized mica surfaces, in each case coated with the amphiphilic protein hydrophobin (HFBI) from Trichoderma reesei. We additionally characterized these surfaces by contact angle measurements and AFM. The results are consistent with the formation of hydrophobic surfaces exposed by HFBI adsorbed on the hydrophilic substrate, and hydrophilic surfaces exposed by HFBI adsorbed on the hydrophobic substrate. In particular, friction between HFBI surfaces on hydrophobized mica, exposing hydrophilic surfaces, is an order of magnitude lower than friction between HFBI-coated hydrophilic surfaces, which expose the hydrophobic side of the protein to the water interface. This result can be readily understood in terms of the greater hydration level of the exposed outer surfaces in the former case.

Phosphatidylcholine (PC) vesicles have been shown to have remarkable boundary lubricating properties under physiologically-high pressures. Here we carry out a systematic study, using a surface force balance, of the normal and shear (frictional) forces between two opposing surfaces bearing different PC vesicles across water, to elucidate the origin of these properties. Small unilamellar vesicles (SUVs, diameters

Using a surface force balance, normal and shear interactions have been measured between two atomically smooth surfaces coated with hyaluronan (HA), and with HA/aggrecan (Agg) complexes stabilized by cartilage link protein (LP). Such HA/Agg/LP complexes are the most abundant mobile macromolecular species permeating articular cartilage in synovial joints and have been conjectured to be present as boundary lubricants at its surface. The aim of the present study is to gain insight into the extremely efficient lubrication when two cartilage surfaces slide past each other in healthy joints, and in particular to elucidate the possible role in this of the HA/Agg/LP complexes. Within the range of our parameters, our results reveal that the HA/Agg/LP macromolecular surface complexes are much better boundary lubricants than HA alone, likely because of the higher level of hydration, due to the higher charge density, of the HA/Agg/LP layers with respect to the HA alone. However, the friction coefficients (μ) associated with the mutual interactions and sliding of opposing HA/Agg/LP layers (μ ≈ 0.01 up to pressure P of ca. 12 atm, increasing sharply at higher P) suggest that such complexes by themselves cannot account for the remarkable boundary lubrication observed in mammalian joints (up to P > 50 atm).

In a series of Surface Force Balance experiments, material from human whole saliva was adsorbed to molecularly smooth mica substrata (to form an 'adsorbed salivary film'). Measurements were taken of normal (load bearing, F_n) and shear (frictional, F_s*) forces between two interacting surfaces. One investigation involved a salivary film formed by overnight adsorption from undiluted, centrifuged saliva, with the adsorbed film rinsed with pure water before measurement. Measurements were taken under pure water and 70 mM NaNO₃. In a second investigation, a film was formed from and measured under a solution of 7% filtered saliva in 10 mM NaNO₃. F_n results for both systems showed purely repulsive layers, with an uncompressed thickness of 35-70 nm for the diluted saliva investigation and, prior to the application of shear, 11 nm for the rinsed system. F_s* was essentially proportional to F_n for all systems and independent of shear speed (in the range 100-2000 nm s^-1), with coefficients of friction μ ~ 0.24 and μ ~ 0.46 for the unrinsed and rinsed systems, respectively. All properties of the rinsed system remained similar when the pure water measurement environment was changed to 70 mM NaNO₃. For all systems studied, shear gave rise to an approximately threefold increase in the range of normal forces, attributed to the ploughing up of adsorbed material during shear to form debris that stood proud of the adsorbed layer. The results provide a microscopic demonstration of the wear process for a salivary film under shear and may be of particular interest for understanding the implications for in vivo oral lubrication under conditions such as rinsing of the mouth cavity. The work is interpreted in light of earlier studies that showed a structural collapse and increase in friction for an adsorbed salivary film in an environment of low ionic strength.

In this paper we review recent work (Goldberg et al.; 2011a,b) on a new use for phosphatidylcholine liposomes: as ultra-efficient boundary lubricants at up to the highest physiological pressures. Using a surface force balance, we have measured the normal and shear interactions as a function of surface separation between layers of hydrogenated soy phophatidylcholine (HSPC) small unilamellar vesicles (SUVs) adsorbed from dispersion, at both pure water and physiologically high salt concentrations of 0.15 M NaNO ₃. Cryo-Scanning Electron Microscopy shows each surface to be coated by a close-packed HSPC-SUV layer with an over-layer of liposomes on top. The shear forces reveal strikingly low friction coefficients down to 2 × 10 ^-5 in pure water system or 6 × 10 ^-4 in the 150 mM salt system, up to contact pressures of at least 12 MPa (pure water) or 6 MPa (high salt), comparable with those in the major joints. This low friction is attributed to the hydration lubrication mechanism arising from rubbing of the highly hydrated phosphocholine-headgroup layers exposed at the outer surface of each liposome, and provides support for the conjecture that phospholipids may play a significant role in biological lubrication.

The roles of macromolecules in living systems as information storage systems (as DNA) and in biochemical synthesis have been much studied and are relatively well understood. Far less is known about their physical behavior at biological surfaces and interfaces. This review considers in particular the roles of polymers in biological lubrication and its relation both to diseases such as osteoarthritis and to remedies such as tissue engineering. The lubricating behavior of common bio-interfacial macromolecules including mucins, hyaluronan, lubricin, and aggrecan are described, and insights into the mechanism of biolubrication are examined in the light of the recently revealed role of hydration lubrication in water-based (including living) systems.

Human salivary statherin was purified from parotid saliva and adsorbed to bare hydrophilic (HP) mica and STAI-coated hydrophobic (HB) mica in a series of Surface Force Balance experiments that measured the normal (F_n) and friction forces (F_s*) between statherin-coated mica substrata. Readings were taken both in the presence of statherin solution (HP and HB mica) and after rinsing (HP mica). F_n measurements showed, for both substrata, monotonic steric repulsion that set on at a surface separation D ~ 20 nm, indicating an adsorbed layer whose unperturbed thickness was ca 10 nm. An additional longer-ranged repulsion, probably of electrostatic double-layer origin, was observed for rinsed surfaces under pure water. Under applied pressures of ~ 1 MPa, each surface layer was compressed to a thickness of ca 2 nm on both types of substratum, comparable with earlier estimates of the size of the statherin molecule. Friction measurements, in contrast with F_n observations, were markedly different on the two different substrata: friction coefficients, μ ≡ ∂ F_s*/∂F_n, on the HB substratum (μ ≈ 0.88) were almost an order of magnitude higher than on the HP substratum (μ ≈ 9 and 0.12 for unrinsed and rinsed, respectively), and on the HB mica there was a lower dependence of friction on sliding speed than on the HP mica. The observations were attributed to statherin adsorbing to the mica in multimer aggregates, with internal re-arrangement of the protein molecules within the aggregate dependent on the substratum to which the aggregate adsorbed. This internal rearrangement permitted aggregates to be of similar size on HP and HB mica but to have different internal molecular orientations, thus exposing different moieties to the solution in each case and accounting for the very different friction behaviour.

Using a surface force balance, we measured normal and shear interactions as a function of surface separation between layers of hydrogenated soy phosphatidylcholine (HSPC) small unilamellar vesicles (SUVs) adsorbed from dispersion at physiologically high salt concentrations (0.15 M NaNO ₃). Cryo-scanning electron microscopy shows that each surface is coated by a close-packed HSPC-SUV layer with an overlayer of liposomes on top. A clear attractive interaction between the liposome layers is seen upon approach and separation, followed by a steric repulsion upon further compression. The shear forces reveal low friction coefficients (μ = 0.008-0.0006) up to contact pressures of at least 6 MPa, comparable to those observed in the major joints. The spread in μ-values may be qualitatively accounted for by different local liposome structure at different contact points, suggesting that the intrinsic friction of the HSPC-SUV layers at this salt concentration is closer to the lower limit (μ = ∼0.0006). This low friction is attributed to the hydration lubrication mechanism arising from rubbing of the hydrated phosphocholine-headgroup layers exposed at the outer surface of each liposome, and provides support for the conjecture that phospholipids may play a significant role in biological lubrication.

Using a surface force balance with fast video analysis, we have measured directly the attractive forces between oppositely charged solid surfaces (charge densities σ+, σ-) across water over the entire range of interaction, in particular, at surface separations D below the Debye screening length λS. At very low salt concentration we find a long-ranged attraction between the surfaces (onset ca. 100 nm), whose variation at D

The very low sliding friction at natural synovial joints, which have friction coefficients of μ

The importance of understanding the interactions between nanoscale materials and living matter has now begun to be appreciated by an extraordinaryly large range of stakeholders, including researchers, industry, governments and society, all of whom appreciate both the opportunities presented by and challenges raised by this arena of research. Not only does it open up new directions in nanomedicine and nanodiagnostics, but it also offers the chance to implement nanotechnology across all industry in a safe and responsible manner. The underlying reasons for this arena as a new scientific paradigm are real and durable. Less than 100 nm nanoparticles can enter cells, less that 40 nm they can enter cell nucleus, and less that 35 nm they can pass through the blood brain barrier. These are fundamental length scales of biological relevance that will ensure that engineered nanoscience will impinge on biology and medicine for many decades to come. One important issue is the current lack of reproducibility of the outcomes of many experiments in this arena. Differences are likely a consequence of such things as uncontrolled nanoparticle aggregation leading to unpredictable doses being presented to cells, interference of the nanoparticles themselves with many of the tests being applied, differences in the degree of confluency of the cells used, and a host of other factors. NanoInteract has shown how careful control of all aspects of the test system, combined with round robin type approaches, can help resolve these issues and begin to ensure that the field can become a quantitative science. The basic principle of NanoInteract is that given identical nanomaterials, cells and biological materials, and using a common protocol, experiments must yield identical answers. Thus, any deviations result from errors in (applying) the protocol which can be tracked and eliminated, until quantitatively reproducible results are obtained by any researcher in any location. This paper outlines the NanoInteract programme, illustrates key advances, and highlights early successes. (www.nanointeract.net)

Includes discussion of "Dynamic properties of confined hydration layers" Susan Perkin, Ronit Goldberg, Liraz Chai, Nir Kampf and Jacob Klein, Faraday Discuss., 2009

We use a surface force balance to study shear interactions between adsorbed poly(ethylene oxide) layers (M_w = 150 000 or 170 000) adsorbed onto mica in 0.1 M KNO₃ aqueous solution. The shear forces increase with increasing compression of the layers or with increasing shear rates (at a constant compression), though at high compressions or shear rates the shear stress σ_s appears to saturate. This behavior is attributed to frictional effects that are dominated by viscous dissipation (and possible weak monomer-monomer complexing) between the mutually sliding layers at low compressions or shear rates, and by a substrate-slip mechanism at the highest compressions and shear rates. The shear behavior of adsorbed PEO layers in aqueous electrolyte at the higher compressions or shear rates can be well understood in terms of the attachment mechanism of PEO segments, via ion ligands to the charged substrate (as elucidated earlier, J. Am. Chem. Soc. 2005, 127, 1104).

Using a surface force balance, we have measured the normal and shear forces between mica surfaces across aqueous caesium salt solutions (CsNO₃ and CsCl) up to 100 mM concentrations. In contrast to all other alkali metal ions at these concentrations, we find no evidence of hydration repulsion between the mica surfaces on close approach: the surfaces appear to be largely neutralized by condensation of the Cs ions onto the charged lattice sites, and are attracted on approach into adhesive contact. The contact separation at adhesion indicates that the condensed Cs ions protrude by 0.3 ± 0.2 nm from each surface, an observation supported both by the relatively weak adhesion energies between the surfaces, and the relatively weak frictional yield stress when they are made to slide past each other. These observations show directly that the hydration shells about the Cs⁺ ions are removed as the ions condense into the charged surface lattice. This effect is attributed to the low energies-resulting from their large ionic radius-required for dehydration of these ions.

We briefly review the model that correlates friction between two surfaces in adhesive contact with the loading-unloading adhesion hysteresis between them. We then examine in light of this model the observed low friction between two mica surfaces coated with a double-chained quaternary ammonium surfactant in intimate adhesive contact in water. This enables us to propose a mechanism for surfactant boundary lubrication in water that is rather different from the classic boundary lubrication in air: in this mechanism, adhesion takes place at the interface between the opposing surfactant hydrocarbon tails, whereas frictional sliding takes place at the interface between the hydrated surfactant headgroups and mica. The implications of our findings to biolubrication processes are discussed.

Analysis of friction versus time traces for stick-slip friction of mica surfaces across solidified films confined between them, reveals that most of the frictional dissipation occurs via viscous heating of the shear melted film during the part of the cycle where the surfaces slide past each other (slip). A much smaller part of the energy dissipation results from the loss of residual kinetic energy at the abrupt end of the slip.

The forces between two adhering surfaces bearing highly extended polymer melt brushes as they are sheared past each other, and between a single melt-brush-bearing substrate sheared across an adhering bare solid surface, were studied using a mica surface force balance with a high shear-force resolution. The melt brushes were created by Langmuir-Blodgett deposition of zwitterion-terminated polyisoprene chains on the mica substrates. Shear of the single melt brush by the bare surface revealed little sliding, deformation, or relaxation of the confined melt brush, under all shear regimes applied in this study. In contrast, shearing of the two melt brushes past each other under the same shear conditions showed a marked shear-rate-dependent, multistage deformation of the sheared brushes. On stopping the applied lateral motion, a logarithmically slow relaxation of the stored stress was observed, which could be quantitatively interpreted in terms of mutual retraction of the entangled tails of the two brushes. The low friction and characteristic relaxation behavior following initial adhesive contact of the brushes developed with time to a solidlike response on shear of the confined chains and was attributed to bridging of chains adsorbed on the opposing surfaces as squeeze-out of the polymer occurred.

Boundary lubrication, in which the rubbing surfaces are coated with molecular monolayers, has been studied extensively for over half a century. Such monolayers generally consist of amphiphilic surfactants anchored by their polar headgroups; sliding occurs at the interface between the layers, greatly reducing friction and especially wear of the underlying substrates. This process, widespread in engineering applications, is also predicted to occur in biological lubrication via phospholipid films, though few systematic studies on friction between surfactant layers in aqueous environments have been carried out. Here we show that the frictional stress between two sliding surfaces bearing surfactant monolayers may decrease, when immersed in water, to as little as one per cent or less of its value in air (or oil). We attribute this to the shift of the slip plane from between the surfactant layers, to the surfactant/substrate interface. The low friction would then be due to the fluid hydration layers surrounding the polar head groups attached to the substrate. These results may have implications for future technological and biomedical applications.

Using surface force balance measurements we have established that polystyrene chains bearing three zwitterionic groups have a higher end-group sticking energy than equivalent chains bearing a single zwitterionic group. In a good solvent, polystyrene chains end-functionalized with three zwitterionic groups form brushes of a higher surface coverage than those bearing a single zwitterion. The increase in surface coverage is slow compared with the initial formation of the brush. Measurements of the refractive index allow us to directly quantify the variation of surface coverage, permitting comparison with models for the kinetics of brush formation based on scaling theory and an analytical self-consistent field. We find qualitative support for associating the kinetic barrier with the energy required for an incoming chain to stretch as it penetrates the existing brush.

The persistant droplet motion in liquid-liquid dewetting was discussed. It was found that the droplet continued to move in all direction of the dewetting front for extended periods with an initial droplet velocity varying linearly with the droplet size. It was observed that the persistant motion was due to a transient surface tension gradient on the substrate liquid surface trailing the dewetting front. A model to calculate the absolute values of the spontaneous droplet displacement and its variation with time was also presented.

Using a mica surface force balance, we have measured the interactions between mica surfaces bearing chitosan (a common, naturally occurring, cationic polysaccharide; the average molecular weight of our sample was 6 × 10⁵, degree of deacetylation 85%) adsorbed from acetic acid solution. We also introduced a polyionic cross-linking agent in order to cause gelation of the adsorbed layer. Both normal and shear interactions (the lateral forces acting between the surfaces as they slide past each other under compression) were measured in the two cases (freely adsorbed and cross-linked chitosan layers). Normal interactions between the adsorbed non-cross-linked chitosan layers were similar to previous reports of interactions between such layers; their shear interactions revealed a very low effective friction coefficient μ_eff = ca. 0.003 at low compressions, increasing to ca. 0.07 at pressures of some atmospheres. We attribute the low friction to the weak interpenetration between the layers arising from steric effects and counterion osmotic pressures, together with the presence of hydration sheaths about the charged polyelectrolyte segments, which are known to provide efficient local lubrication. The higher friction on strong compressions is attributed to bridging effects. For the case of the cross-linked layer, normal interactions revealed longer ranged and more repulsive forces, due probably to the network formation resulting in a higher effective modulus of the layers. Frictional forces between the rubbing cross-linked layer were much higher than for the non-cross-linked chitosan, an effect we attribute to increased segmental friction arising from attractive interactions between the cross-linking points; this is also consistent with our observation that for the cross-linked layers significant hysteresis was observed when measuring normal interactions on approach and separation of the layers, an effect that was absent for the case of the non-cross-linked adsorbed layers. Refractive index measurements revealed an adsorbance of 1.2 ± 0.4 mg/m² of the polymer on each mica surface, consistent with expectations for cationic polymers adsorbed on solid surfaces.

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. 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. This behaviour is attributed to the tenacity of the hydration sheaths together with their rapid relaxation time. Finally, a very recent study 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.

A surface force balance has been used to investigate the viscosity of salt-free (conductivity) water confined between hydrophilic and between hydrophobic surfaces. We examine the process of jump-in, across the last few nanometres of thin water films, to adhesive contact between the surfaces. We analyse the flow of water out of the gap under slip and no-slip boundary conditions at the confining surfaces. In both cases we find that the effective viscosity of water remains comparable to its bulk value even when it is confined to sub-nanometre thin films.

We have measured the shear forces between solid surfaces sliding past each other across aqueous salt solutions, at pressures and concentrations typical of naturally occurring systems. In such systems the surface-attached hydration layers keep the compressed surfaces apart as a result of strongly repulsive hydration forces. We find, however, that the bound water molecules retain a shear fluidity characteristic of the bulk liquid, even when compressed down to films 1.0 ± 0.3 nanometer thick. We attribute this to the ready exchange (as opposed to loss) of water molecules within the hydration layers as they rub past each other under strong compression.

An investigation of the time-dependent behavior of the normal forces between two smooth mica surfaces immersed in salt-free water was presented, using a surface force balance (SFB). An equilibrium surface-charge density σ = σ₀ was indicated by a long-ranged repulsion on initial approach to adhesive contact. The results showed that subsequent force measurements at times τ following separation of the surfaces revealed drop in σ, followed by contact and separation, but then relaxed back to σ₀ with a characteristic time τ_r = 11 ± 2 minutes.

The fluidity of water in confined geometries is relevant to processes ranging from tribology to protein folding, and its molecular mobility in pores and slits has been extensively studied using a variety of approaches^1-6. Studies in which liquid flow is measured directly suggest that the viscosity of aqueous electrolytes confined to films of thickness greater than about 2-3 nm remains close to that in the bulk^7-9; this behaviour is similar to that of non-associative organic liquids confined to films thicker than about 7-8 molecular layers^8,10,11. Here we observe that the effective viscosity of water remains within a factor of three of its bulk value, even when it is confined to films in the thickness range 3.5 ± 1 to 0.0 ± 0.4 nm. This contrasts markedly with the behaviour of organic solvents, whose viscosity diverges when confined to films thinner than about 5-8 molecular layers^10-15. We attribute this to the fundamentally different mechanisms of solidification in the two cases. For non-associative liquids, confinement promotes solidification by suppressing translational freedom of the molecules^11,15-18; however, in the case of water, confinement seems primarily to suppress the formation of the highly directional hydrogen-bonded networks associated with freezing^1,3.

The forces between layers of poly(ethylene oxide) (PEO), of molecular weights M = 37 × 10³ (PEO37) and M = 112 × 10³ (PEO112) adsorbed onto smooth, curved solid (mica) surfaces across the good solvent toluene have been determined using a surface force balance (SFB). The SFB used is capable of measuring both normal interactions F_n(D) as a function of surface separation D and, with extreme sensitivity, shear or frictional forces F_s(D,ν_s) between them as they slide past each other at velocity ν_s. The F_n(D) profiles are closely similar to those measured in earlier studies between adsorbed PEO layers. The shear or frictional forces between the sliding PEO-bearing surfaces are very low up to moderate compressions of the adsorbed layers (local pressures up to ca. 10⁵ N m^-2), corresponding to effective friction coefficients μ_eff = (F_s/F_n) of order 0.003 or less. This is attributed to the fluid interfacial layer between the adsorbed layers resulting from their weak mutual interpenetration. At higher loads F_s increases markedly, and two forms of behavior are found depending on the PEO molecular weight. For PEO37, a sharp increase in F_s is followed by removal of polymer from within the intersurface gap during sliding, high friction, and adhesion between the surfaces. For the longer PEO112, the initial increase in F_s and in μ_eff saturates at the highest loads (for the case of μ_eff even decreasing), indicating that the slip plane has moved from the polymer/polymer midplane to the polymer/ solid interface. The dependence of F_s on the sliding velocity in the high-friction regime is weak, suggesting that at low compressions there is a thinning of the mutual adsorbed-layer-interpenetration region at high ν_s that offsets the higher viscous dissipation in that region. At the highest loads, when the slip plane has shifted to the mica surface, the weak F_s(ν_s) dependence is characteristic of sliding friction at solid substrates.

We have confirmed the existence of the BeC62- dianion produced in a Cs-sputter negative ion source with a cathode of mixed Be metal and graphite powder. Using our laser-accelerator mass spectrometry (AMS) system, we have studied the photoelectric interaction of the dianion and show that it is bound by more than 1.165 eV relative to any photodetachment or dissociation channel. The total cross-section leading to either of the channels for 2.33 eV photons is 6 Mb. (C) 2000 Elsevier Science B.V. All rights reserved.

The interactions between two mica surfaces bearing a fourth-generation carbosilane dendrimer (modified to expose -OH groups on its outer surface) were studied across a toluene medium, using a surface force balance capable of measuring shear as well as normal forces. Normal force measurements indicate that the dendrimers adsorb from dilute toluene solution (ca. 5×10^-4 w/w) as a monolayer on each surface. Two such interacting surfaces experience a longer-ranged van der Waals attraction followed by strong short-range adhesion (probably of dipolar origin) as the adsorbed dendrimers come into contact. Within the range of our parameters, the dendrimer layers were incompressible normal to the surfaces. Friction versus load profiles were measured at different shear velocities, revealing marked stick-slip sliding, whereas the magnitude of the yield stress increased with longer times of contact and with normal pressure. This suggests that over time scales comparable with the experimental times the interacting layers rearrange to optimize their interfacial shear strength. The behavior of these -OH-exposing carbosilane dendrimers differs qualitatively from that of CH₃-exposing poly(propyleneimine) dendrimers studied earlier, a difference attributable to the much more polar nature of the hydroxyl groups.

We have used composition depth profiling, based on nuclear-reaction analysis and secondary ion mass spectroscopy, to study segregation at the free surface of a partly miscible binary mixture consisting of random olefinic copolymers. The equilibrium surface excess data, analysed within a mean-field Cahn approach, point to a wetting transition. The surface phase diagram obtained was confirmed by the observed dynamics of the segregation from a coexistence composition: the monotonic and halted growth of the surface layer was observed at temperatures above and below the predicted wetting point, respectively.

We compare segmental interaction parameters χ_AB in binary polyolefin mixtures extracted from a fit to the binodal-as deduced from composition-depth profiling of thin films-with values extracted from small-angle neutron scattering (SANS), on the self-same blends. We find good quantitative agreement as regards both absolute values and compositional dependence of χ_AB. We also compare values of χ_AB obtained from composition-depth profiles of surface segregation in isotopic polystyrene mixtures with values deduced from SANS from these mixtures, and again we find good agreement between them. These results point to the use of thin-film composition-depth profiling, which is potentially a more accessible technique and requires far smaller quantities of material, as a convenient, accurate, and widely applicable alternative to SANS for measuring segmental interactions in binary polymer mixtures.

Based on segregation data, determined with profiling techniques, we analyze surface phase diagram of binary liquid mixtures composed of random olefinic copolymers. Blends with extended- and small- critical point wetting regimes are discussed. First observation of wetting transition is presented. Surface enrichment-depletion duality, a phenomenon prerequisite to the 2nd order wetting transition, is described.

According to a common viewpoint the surface of the binary polymer mixture A/B could be enriched only in one component, say A, regardless of the value of its bulk volume fraction φ_bulk. From recent theoretical analyses and Monte Carlo simulations one can expect however that some mixtures can exhibit surface segregation in the minority blend component, i.e. enrichment in the component A for φ_bulkbulk > 50%. Using composition-depth profiling techniques, we have observed both types of the segregation with only one- or both-blend component(s) preferred at the surface. These results were obtained for model mixtures composed of partly deuterated (dx) and protonated (hx) random olefinic copolymers of the structure -[C₄H₈]_1-x [C₂H₃(C₂H₅)]_x(-). A simple mean-field model is presented to explain both situations.

The forces between two surfaces bearing solvated, telechelic polymer chains (terminated at both ends with a dipolar group) exhibit a clear attractive regime. The range and magnitude of this attraction indicate the presence of multimers on each surface, and the formation of entropically favored bridges between them as the telechelic layers overlap. On sliding the surfaces a shear force close to that expected from the stretching of the polymer bridges is observed, suggesting that the frictional forces can be tuned by varying the interaction strength of the telechelic end groups.

The evolution of pre-rupture undulations at the liquid-air interface of thin non-wetting liquid films spread on a solid substrate was monitored in real time by non-perturbative interference microscopy. The spatial distribution of the incipient undulations is non-random and characterized by a typical wavelength, as predicted for van der Waals unstable films, despite the fact that the system is expected to be vdW-stable, and that ultimate dewetting of films appears to take place via a heterogeneous nucleation mechanism.

We have extended earlier work on the reduction of friction by polymer brushes between moderately-compressed sliding surfaces to the case of shear forces between brush-bearing surfaces as they slide past each other at high compressions, against much larger frictional forces. Our results reveal that at compression ratios β = (2L/D) ≥ 8, where L is the unperturbed thickness of each brush and D the surface separation, the shear forces rise rapidly. At sufficiently high compressions (β ≥ 10) we observe stick-slip behavior, as well as clear indications of detachment of the chains from the surfaces for the case of the shortest brushes. Closer examination of the data shows that at lower compressions (8 ≥ β ≥ 10) the sliding occurs within the overlapped polymer layers, and the friction is due to viscous drag on the interpenetrated polymer moieties. At the highest compressions - corresponding to the highest frictional forces - our data suggest that the sliding may take place by slip at the polymer/substrate interface, as the bonds anchoring the chains to the substrate detach and reform.

Motivated by recent experiments on the sliding of two surfaces separated by ultrathin films of simple organic liquids, we analyse the shear and resulting dynamics of the confined materials. Our results indicate that the effective viscosity of shear-melted thin films of such liquids is low, and can account for several features of the experimental results, including the observation of stick-slip effects up to high shear rates. Our analysis also points to the origin of the frictional dissipation between sliding surfaces separated by thin films of simple liquids.

A surface force balance with extremely high resolution in measuring shear forces has been used to study the properties of films of the simple organic solvents cyclohexane, octamethylcyclotetrasiloxane, and toluene, confined in a gap between smooth solid surfaces. We were able to probe in detail the transition between liquidlike and solidlike behavior of the films as the gap thickness decreased. Our results reveal that in such confined layers the liquids are fluid down to a film thickness of few molecular layers (typically seven, depending on the particular liquid examined). On further decreasing the gap thickness by a single molecular layer, the films undergo an abrupt transition to become solidlike in the sense that they are able to sustain a finite shear stress for macroscopic times. At the transition, the effective rigidity of the films, quantified in terms of an effective creep viscosity, increases by at least seven orders of magnitude. This sharp transition is reversible and occurs as a function of the confinement alone: it does not require external applied pressure. Following the transition the confined films behave under shear in a manner resembling ductile solids.

A detailed analysis of the experimental implications of the scaling theory of polymer adsorption in the good solvent regime is presented. A number of new results that simplify the task of comparing theoretical predictions and experimental data are given: these include a new simple approximate expression for the force vs distance profile, which is close to the exact solutions over an appreciable range of the intersurface separations. The theoretical predictions are compared to available experimental data for the forces arising between mica plates exposed to poly(ethylene oxide) - water solutions. Good quantitative agreement between theory and experiment is found, with no need for adjustable parameters.

The concentration profiles of high molecular weight, isotopic polystyrene blends in the near-surface region were directly measured using real-space composition-depth profiling based on nuclear reaction analysis. The measured profiles are in good agreement with predictions of the Schmidt-Binder mean field theory. In contrast to previous indications, we find no evidence for a flattening of the concentration profile near the surface.

Thin liquid oligostyrene films on top of a surface-anchored, polystyrene brush-solvated by the oligostyrene itself - roughen spontaneously. Using optical phase-interference microscopy and nuclear reaction analysis we have characterized the topography of such roughened films. We see that the undulations formed reach down at most to approximately the top of the solvated brush, but not to the underlying solid substrate on which the brush is anchored. Possible origins for this behaviour are discussed in terms of a picture wherein the solvated brush is regarded as a quasi-solid substrate for the liquid film on top.

We have measured the growth with time t of a wetting layer (of thickness l(t)) at the surface of a thin film of a binary liquid (polymer) mixture. Over a wide range of experimental parameters, our data is well described by a model of diffusion limited wetting which takes into account the finite film thickness. In this model, l(t) is a function of time which sensitively depends on the nature of the interfacial potential: a detailed comparison shows that long range van-der-Waals forces provide the main driving force for the build-up of the wetting layer.

Surface segregation in thin films of binary liquid mixtures consisting of random olefine copolymers was studied by nuclear reaction analysis over a wide temperature and composition range. A divergence of the surface excess Γ was indicated as the binodal of each mixture was approached from the one-phase region, even at temperatures 100 °C below the critical point T_c, and interpreted as the advent of complete wetting behavior. A consistent description of the adsorption isotherms in terms of a mean field approach assuming a short-ranged surface potential f_s is feasible, but requires an unexpected temperature dependence of f_s. This dependence causes the wetting transition temperature to be located lower than expected on the basis of present models.

We have used composition depth profiling of polymer bilayers, based on nuclear reaction analysis, to determine miscibility, phase coexistence, and critical temperatures in mixtures of random olefinic copolymers of mean composition E_1-x/EE_x; here E is the ethylene group -(C₄H₈)-, EE is the ethylethylene group -[C₂H₃(C₂H₅)]-, and one of the copolymers is partially deuterated. The components in each binary mixture have different values x₁,x₂ of the EE fraction. Using a simple Flory-Huggins mixing model, our results enable us to extract an interaction parameter of the form χ(x₁,x₂,T)=A(x₁,x₂)/T, where for given x₁,x₂, A is a constant. Calculated binodals using this form fit our measured coexistence curves well, while allowing χ a weak composition dependence improves the fit further. Within the range of our parameters, our results suggest that in such binary polyolefin mixtures the interaction parameter increases roughly linearly with the extent of chemical mismatch expressed as the difference in degree of ethyl branching between the two components.

When a film of thickness D of a binary mixture on a substrate segregates into two coexisting phases, an interface between the phases parallel to the substrate may form due to preferential surface attraction of one of them. It is argued then that the correlation length [Formula presented]for interfacial fluctuations parallel to this interface [Formula presented] leads to a size-dependent interfacial width [Formula presented]. Nuclear reaction depth profiling experiments on polymer mixtures as well as Ising model simulations both support this prediction.

We have examined the growth with time t of the thickness l of wetting layers from thin films of binary fluid mixtures, using real-space composition-depth profiling based on nuclear reaction analysis. We find over a wide range of parameters that the observed growth behavior has a power law form l∝t^k, where k is the range 0.20.3. Comparison with the predictions of a diffusion-limited wetting model shows that growth of the wetting layers is driven primarily by long-ranged surface fields.

Interfacial adsorption from a binary mixture of short and long polystyrenepolyisoprene diblock copolymers (PS-PI or its deuterated analogue dPS-PI) to interfaces of a PS(M = 3 × 106) homopolymer was studied using nuclear reaction analysis. Short symmetric diblocks dPS(M = 10⁴)-PI(M = 10⁴) (designated dS), or a similar protonated analogue (hS), and a highly asymmetric, long diblock dPS(M = 10⁶)PI(M = 10⁴) (L) were used in the binary mixtures. We found that the shorter diblocks adsorb preferentially at the interfaces: the isotopic contrast between dS and hS in the mixtures with L enables us to extract detailed information on the surface segregation of the short and long species. Our data are analyzed in terms of a modified Flory-type mean field model due to de Gennes and Leibler. Interfacial segregation from the binary diblock mixture is well predicted by this model with no adjustable parameters, using the adsorption characteristics determined earlier for systems with a single diblock component.

We have used nuclear reaction analysis to measure diffusion coefficients D in couples consisting of hydrogenated polybutadienes of structure (C₂H₃(C₂H₅))_x(C₄H₈)_1−x and their partly deuterated counterparts. The 1,2 and 1,4olefinic isomers are randomly distributed along the chains and the mean vinyl fraction x varies between 0.38 and 0.94. We find that the effective monomeric mobility D₀ [defined by D = D₀(N_e/N²) for each copolymer, where N is the backbone length and N_e the entanglement spacing] decreases monotonically with increasing vinyl content x. Over the range of microstructures and temperatures T (−14−40°C) investigated we find log(D₀/T) varies smoothly with (T − T_g), where T_g is the glass transition temperature of the respective melts. An analysis of our data in terms of a simple activated rate process model suggests that D₀ is controlled by thermally activated hopping of segments whose effective volume is close to that of the respective statistical segment lengths of the copolymeric chains. ©1995 John Wiley & Sons, Inc.

We have used a recently developed surface force balance to measure, with extreme sensitivity, both lateral and normal forces between interacting surfaces, for the case of simple liquids and particularly with surfaceattached polymers. The presence of polymers on the surfaces reduces drastically the force required to maintain them in sliding motion, under a given normal load, relative to the bare surface case. We believe this is due to the long range steric repulsion which can sustain a large normal load while maintaining a very fluid interfacial layer. The effect is much more marked for endtethered chains in a good solvent than for adsorbed chains in a θsolvent. This is attributed to the different extents of interpenetration of the compressed polymer layers.

The way in which flexible polymers can modify the structure of a coated surface has been studied by measuring the interactions between polymer-bearing surfaces in liquids. It is observed that interactions induced by polymers attached to surfaces can also lead to striking changes in the effective 'wetting' properties of thin liquid films. A film is said to 'wet' a surface if it tends to spread uniformly on a solid surface. The smoothness and long-term stability of such films depends on how well they wet the surface, and this is essential for the electronic and electro-optical devices, for example, to work properly. If the films are to break up or 'dewet' the surface, the device would be of little use.

The diffusion process in dPS (M_w = 1.06 × 10⁶ g mol^-1)/hPS (M_w = 2.89 × 10⁶ g mol^-1) mixtures at constant temperature below the critical temperature slows down approaching the coexistence curve from the homogeneous single fluid phase region of the phase diagram. This effect can be understood in terms of the composition dependence of the thermodynamic factor (∂μ_dPS/∂Φ_dPS)_T,P in combination with the Flory-Huggins theory of polymer melts. The theoretically expected decrease of the mutual diffusion coefficient with increasing temperature along the coexistence curve approaching the critical temperature is not observed in the temperature range studied (5 K c - T)

Stabilization against the rupture and breakup of thin, nonwetting liquid films spread on surfaces is generally sought by modification of equilibrium interfacial properties. A mechanism for suppressing rupture in such films that uses surface-attached polymers together with free chains in the bulk of the film is reported. Films of an oligostyrene liquid, which rupture within several minutes when spread on a silicon wafer, may be stabilized for many months by a polystyrene brush attached to the substrate, together with some free polystyrene in the liquid. The effect may arise from entanglements of the free chains with the immobilized brush.

Critical point wetting generally occurs whenever a binary fluid system in the demixed region of phase space, in contact with a surface, approaches its critical temperature. For the case of polymeric mixtures the segmental interaction parameter, which determines the interfacial tension between the coexisting phases, can be very low even far from the critical point. This suggests that polymer blends should be likely candidates to exhibit complete wetting even far below the critical point. Using nuclear reaction analysis, we have now observed such complete wetting behaviour from two different classes of binary polymer mixtures. These are mixtures of statistical olefinic copolymers, with slightly different chemical microstructures; and an isotopic pair of deuterated and protonated polymers. In the former case we have been able to follow the growth with time t of the wetting layer thickness l; our results indicate l approx. log t.

Keywords: Chemistry, Physical; Physics, Condensed Matter; Polymer Science

A thin bilayer of two coexisting polymer phases, in contact with a surface which favors and is partially wetted by one of them, was studied by nuclear reaction analysis and phase contrast microscopy. We find that when the less-favored phase is initially in contact with this surface, it is entirely replaced by the partially wetting phase. This inversion evolves with time very differently than in the case of complete wetting. The results suggest that a microscopic surface layer enriched in the surface-preferred component may not be a stable signature of partial wetting in small binary mixtures.

A model is developed which explains a recently-observed asymmetry in the phase-equilibrium behavior of mixtures of statistical ethylene (E)/ethylethylene (EE) copolymers [formula omited], with differing microstructure and isotopic substitution levels. A coupling between the isotope and the microstructure contributions to the overall effective segmental interaction parameter χ is predicted, which could enhance or reduce χ depending on the ethylene content of the protonated component relative to that of the deuterated one. From the overall χ, the theory permits the extraction of the bare isotope interaction parameter χ_h/d between hydrogenated and deuterated species and of the parameter χE/EE for the E/EE interaction. This is done for the recent data set on coexistence in E/EE mixtures obtained by Eiser et al. The parameters thus estimated are compared with available experimental data on similar polyolefinic mixtures.

Using surface force measurements, we have determined the structure of polymer brushes formed onto mica, from dilute solutions of zwitterion-terminated polystyrene chains of molecular weights 26 500 and 375 000 in the good solvent toluene. We find that brushes of the longer amphiphiles, formed from a solution of these polymers alone, are rapidly replaced by shorter chains when the latter are added to the solution. This requires a certain minimum concentration of the shorter amphiphiles, but substantial replacement of long-by-short chains can occur even when the monomer concentrations of the shorter polymers is only (1/500) that of the longer ones. By analyzing the force profiles for the mixed brushes thus formed, we obtain a quantitative measure of their structural details. We evaluate these observations in terms of a simple scaling model for the free energy of brushes that are in equilibrium with free end-functionalized chains in solution.

Coexisting polymer phases are characterized by very small interfacial energies, even well below their critical solution temperature. This situation should readily lead to the exclusion of one of the phases from any interface that favors the other. Such complete wetting behavior from a binary mixture of statistical olefinic copolymers is reported. By means of a self-regulating geometry, it is found that the thickness of a wetting layer of one of the phases at the polymer-air interface, growing from the other coexisting phase, attains macroscopic dimensions, increasing logarithmically with time. These results indicate that binary polymer mixtures could be attractive models for the study of wetting phenomena.

The use of optical second harmonic generation (SHG) to probe, in situ and in real time, the physical grafting of polymers from dilute toluene solution onto mica crystal surfaces is reported. Despite using polymers with no hyperpolarizable groups, and the very low surface density of end-attached species, we show how changes in the SHG signal of the substrate may be monitored during polymer grafting. Characteristic attachment rates are obtained by this method.

We describe a method for directly determining the composition profile of deuterated polymer chains in polymer mixtures. Our technique, nuclear reaction analysis, is based on the ²H(³He, ⁴He)¹H nuclear reaction. By detecting ⁴He in a forward geometry, we achieve a spatial resolution of 14 nm (FWHM). We use this technique to probe the broadening of the interface between two partially miscible polymers. We found that such a system attains a finite interfacial width in equilibrium. For short times, we monitor the dynamics of interface formation. We found that the interfacial width increases significantly slower than in the case of free diffusion.

ADSORBED or grafted polymers are used to control phenomena such as colloidal stability, fluid flow and the tribological properties of surfaces. Forces between polymer-bearing surfaces have been studied comprehensively over the past decade^1-10, but little is known about such forces in shear. These are intimately related to the dynamic as well as the equilibrium properties of the surface-attached chains. We have constructed a device that measures directly the forces that act between surfaces bearing polymer layers in a liquid medium as they slide past each other. For the case of mica sheets bearing end-grafted chains of polystyrene in toluene (a good solvent), we find that, as the surfaces move parallel to each other, there is a marked change in the normal forces between them. These become increasingly repulsive at higher velocities. The effect occurs only above certain critical shear rates, probably related to relaxation dynamics of the end-grafted chains themselves. Our findings have direct implications for the properties of polymeric lubricants, and for the rheological behaviour both of stabilized dispersions and of multi-phase polymeric systems.

We discuss the nature of the initial interactions as two polymer-bearing surfaces in a good solvent approach each other, as measured directly by the mica force apparatus. It is suggested that, while for grafted chains and for adsorbed chains at low surface coverages these initial interactions are probably well described by constrained-equilibrium models, this may not be the case for adsorbed chains at high surface coverages.

We have measured the forces between mica surfaces immersed in cyclopentane (CP) in the presence of linear (LPS) and cyclic polystyrene (CPS) chains of similar molecular weights, a few degrees above the Θ-point of the LPS/CP system: while LPS adsorbs (in accordance with earlier studies), CPS does not adsorb under the same conditions. This is likely to be due to differences in the thermodynamics induced by the different topologies of the two types of polystyrene chains.

The adsorption of polymers onto a surface from a θ solvent is treated in terms of a mean- field model based on a Cahn-de Gennes approach. In particular, we calculate the forces between two such polymer bearing surfaces and compare our results in some detail with available experimental data on force profiles between mica surfaces bearing adsorbed polymer near the θ temperature. All parameters in our model may be estimated from experiment. The predicted force profiles are in very good qualitative agreement with the experimental data, though the absolute spatial and energy scales are smaller for the calculated profiles by factors of ca. 4 and 2.5 relative to experiment. The causes of this discrepancy and possible improvements to the model are considered.

In the last decade there has been considerable advancement in the understanding of the role played by adsorbed polymers in modifying the forces between surfaces. This development has been both theoretical and experimental and the two have advanced largely in parallel. In this paper we report the forces observed between adsorbed layers of poly(ethylene oxide) of molecular weight 1.2 × 10⁶ at both partial coverages of adsorbed polymer, where an initial attractive force is measured, followed by a shorter-range repulsion and at full surface coverages, where a long-range, essentially osmotic, repulsive force is noted. The attractive forces observed at low surface coverages are attributed to polymer bridging and are qualitatively similar to the predictions of both mean-field and scaling treatments. The force-distance profiles on initial interaction between the fully covered surfaces resemble those predicted and observed for dangling, end-anchored chains.

We have directly measured the interface formation and diffusion between two partially miscible polymers, SCPE and PMMA, using Rutherford backscattering spectrometry, as the temperature was varied from the glass transition into the two-phase region. As the temperature was increased, the interfacial width for a given diffusion time increased sharply, attaining a maximum value approximately 25 °C above the lower critical solution temperature and then dropped abruptly. The results are briefly discussed within the framework of the extended Flory-Huggins theory wherein nonlocal terms are included in the free energy.

The adsorption of high polymers modifies the short-range forces between surfaces in liquid media and is widely used to stabilize or flocculate colloidal dispersions¹. Previous studies have shown that low surface-coverage by the polymer leads to long-range bridging attraction between the surfaces ², whereas repulsion sets in at high adsorbance in good solvents ^3,4. In addition, marked hysteresis has been observed for both adsorbed homopolymers and co-polymers on approach and rapid separation of the surfaces^3-5. Here we report the direct measurement of forces between terminally anchored, non-adsorbing polymer chains (polystyrene) in good solvents (toluene and xylene). The polymer layers are found to extend some 6R _g (where R_g is the unperturbed radius of gyration of the polymer) out from each surface, substantially further out than adsorbing homopolymers. Monotonically increasing repulsive forces are observed as the surfaces approach each other and there is no evidence of bridging attraction at low-surface coverage. In addition we find that the force law is reproducible and independent of compression/decompression rates, in marked contrast with adsorbed homopolymers.

Self-diffusion in polymer melts has been extensively studied and is reasonably well understood in terms of the reptation model^1-4; the related phenomenon of mutual diffusion in miscible blends of chemically different polymers has received little attention, despite its practical relevance and implications for physical processes, such as phase separation kinetics. In such blends, attractive interactions between the monomers, when summed over a polymer chain, may lead to large enthalpic driving forces favouring the mixing; this in turn results in a mutual diffusion rate which is rapid compared with the entropically driven self-diffusion⁵, and which is strongly composition-dependent⁶. We have measured mutual diffusion as a function of composition in one such binary blend, polyvinyl chloride (PVC)/polycaprolactone (PCL), and report here that the mutual diffusion coefficient is strongly enhanced in the middle of the composition range. This result is qualitatively, though not quantitatively, in accord with the results of some recent theoretical treatments^5-8.

Analytical expressions, based on a mean-field model and derived in a previous paper (part 1: Klein, J.; Pincus, P. A. Macromolecules 1982,15,1129), for the interaction between two parallel plates bearing adsorbed polymer in poor-solvent medium, are solved numerically to yield (a) segmental density profiles of the adsorbed polymer and (b) interaction-energy vs. plate-separation profiles. All parameters appearing in these calculations are obtainable from bulk data such as the polymer-solvent phase diagram and adsorbance measurements. The calculated results are critically compared with model experiments on forces between smooth mica surfaces bearing polystyrene in cyclohexane in poor-solvent conditions: the agreement is qualitatively very good and quantitatively fair. Some improvements to the model are suggested.

Forces between polystyrene layers absorbed on mica and immersed in cyclohexane have been measured. The measurements were made on two different molecular weights (6 X 10⁵ and 9 X 10⁵) in two different laboratories and therefore support the quantitative reliability of the results. We have reproduced previous results of this type of measurement below the θ temperature and extended the force measurement to (a) adsorbed layers at lower surface coverage and (b) temperatures above the bulk polystyrene-cyclohexane θ temperature. At a coverage of about 1.1 mg/m² of polystyrene, which is on the order of 20-30% of saturation, we found strongly attractive forces below T_θ, detectable at separations of about 300 Å between the bare mica surfaces. The forces can be measured very accurately and precisely in this situation. The force reaches a minimum at 46 ± 2 Å and becomes strongly repulsive closer in. The long-range attractive portion of the force curve is very nearly exactly exponential, with a decay length of 45 ± 2 Å. For saturated surfaces with about 4.5 ± 1 mg/m² the force is detectably attractive at larger distances (600-1200 Å) both below (23 and 26 °C) and above (37 ± 2 °C) the temperature (34.5 °C). For each molecular weight the positions of the minimum in the F(D) curve and of the short-range repulsive barrier are at smaller separations at T > T_θ. The magnitudes of the minima are smaller at T > T_θ as well. Both of these new results suggest strongly that the forces, especially the attractive components, between the polymer surfaces are influenced by effects in addition to the usual segment-segment interactions which determine bulk thermodynamic properties.

The dynamic properties of concentrated solutions and melts of linear polymers are reasonably well understood in terms of the reptation concept, whereby molecules are constrained to curvilinear motion within 'tubes' formed by entanglements with their neighbours^1-3. Understanding of dynamics of entangled nonlinear polymers, however, is still rather limited. Reptation in such cases is expected to be strongly suppressed, but there is little direct evidence for this, and conflicting models have been proposed^4-6. We report here a critical study of the diffusion coefficient D of a series of model linear and three-arm star-branched polymers, diffusing in an entangled linear polymer melt matrix, designed to elucidate dynamic mechanisms for the entangled stars. Measuring D as a function of diffusant degree of polymerization N we find, for the linear molecules, D ∝ N^-2, as expected for purely reptative motion^1,7-9. For the case of moderately short stars, however, D falls considerably faster than an inverse square power law, and is well fitted by an exponential type relation D ∝ e^-αN. There is evidence that for the longest stars used in the present study it is the release of entanglements by reptation of the linear matrix molecules which dominates the dynamics. This is the first direct indication of such 'tube-renewal' effects in a system of entangled polymers⁸.

The forces between mica surfaces a distance D apart immersed in cyclohexane, bearing adsorbed layers of polystyrene, have been measured at temperatures lower than the corresponding critical temperatures. Polymers of two different molecular weights were used. The results show that these forces are attractive for 3R_g > D >. R_g (where R_g is the polymer radius of gyration) and repulsive at lower D, and may be understood in terms of the phase equilibrium of the polystyrene-cyclohexane system. The adsorption of the polymer under these conditions appears to be effectively irreversible over the time of our experiments. The adsorbance of polymer and the thickness of the adsorbed layers are comparable with values measured in other studies using entirely different techniques.

The rates at which molecular sequences may deposit onto growing lamellae in a crystallising polyethylene melt are examined on the basis of the results of recent self-diffusion experiments in such melts, in conjunction with theories of molecular dynamics in polymer melts based on the reptation picture. The results are compared with rates of sequence deposition in polyethylene melts as estimated from experimentally measured growth rates. This comparison indicates that, purely from a kinetic point of view, some regular folding of molecular trajectories at lamellar surfaces is not incompatible with experiment.