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Hypothesis Adsorption of polyelectrolyte brush-grafted nanoparticles (BGNPs) produces a heterogeneous interface with sub-monolayer surface coverage resulting from lateral electrostatic repulsions that limit packing. As a result, the interaction forces between opposing BGNP layers include an adhesive cross-surface BGNP-substrate bridging force that depends on the interparticle spacing, particle size, and strength of electrostatic interactions. We hypothesize that BGNPs with pH-responsive, annealed polyelectrolyte brushes can undergo controlled changes in surface area coverage through post-adsorption swelling or de-swelling into non-equilibrium layer conformations and that such changes in surface coverage can switch off or switch on particle intercalation, bridging attractions, and enhanced energy dissipation upon sliding. This work aims to characterize the nature of surface forces in heterogeneous BGNP adsorbed layers and to utilize pH-sensitive bridging forces as a mechanism to tune friction and adhesion. Experiments Colloidal probe atomic force microscopy (CP-AFM) is used to measure normal and lateral forces between negatively charged silica surfaces with adsorbed pH-responsive cationic BGNPs. The BGNPs are poly(2-dimethylaminoethyl methacrylate) brush-grafted silica nanoparticles. Adhesion force and friction analysis is complemented by simultaneous quartz-crystal microbalance and ellipsometry measurements under conditions that render the particles strongly charged and swollen (acidic) or weakly charged and de-swollen (basic). Findings Adsorbed BGNPs can be swollen or de-swollen via pH rinses, enabling direct control of surface coverage and bridging interactions. Transitions from adhesive bridging contacts with high friction to non-adhesive contacts with low friction forces occur when adsorbed BGNP layers are switched from a de-swollen/weakly charged state to a swollen/highly charged state. The ability to controllably shift the character of normal and lateral forces via coverage-mediated bridging interactions is a unique feature of adsorbed nanoparticulate brush constructs and highlights their potential to condition surfaces with additional functionality compared to dense, planar homopolymer brushes. [ABSTRACT FROM AUTHOR]

This work investigates surface forces that result from adsorbed layers of silica nanoparticles with grafted pH-responsive, cationic poly(2-(dimethylamino)ethyl methacrylate) brushes (SiO2-g-PDMAEMA) and how adhesive bridging forces can be suppressed and friction forces reduced by "backfilling" these heterogeneous adsorbed layers with nonionic poly(ethylene oxide) star copolymers (Star PEO45MA). Adsorption of SiO2-g-PDMAEMA and Star PEO45MA to silica is measured as a function of pH by quartz crystal microbalance with dissipation (QCM-D) in order to evaluate the electrostatically driven adsorption of SiO2-g-PDMAEMA and hydrogen-bonding-driven adsorption of Star PEO45MA. Force measurements performed using colloidal probe force microscopy show the strong role that limited surface coverage plays in adhesive bridging forces between silica with adsorbed SiO2-g-PDMAEMA, while Star PEO45MA adsorption produces purely repulsive steric interactions. Bridging between SiO2-g-PDMAEMA-coated surfaces produces frictional forces that tend to be larger than those acting between bare surfaces at similar normal loads, while friction is consistently decreased by Star PEO45MA adsorption. Sequential adsorption of SiO2-g-PDMAEMA and Star PEO45MA generates high-coverage mixed nanoparticulate brush layers with uniformly repulsive normal forces and reduced friction forces. Adsorption and force measurements reveal that Star PEO45MA not only adsorbs to silica but also binds to SiO2-g-PDMAEMA. The latter allows sequential adsorption of the two components to produce mixed multilayers. The mixed SiO2-g-PDMAEMA/Star PEO45MA multilayers exhibit larger layer thicknesses, no bridging, and sustained smooth friction, highlighting their potential usefulness as aqueous boundary lubricant layers. [ABSTRACT FROM AUTHOR]

Dopamine-melanin (DM or "polydopamine") can be deposited on virtually any substrate from solution through autoxidation of dopamine. The versatility of this process has allowed surface-mediated assembly of DM for a wide variety of functional coatings. Here we report the impact of well-defined surface chemistries on the nucleation and growth of such films. DM was deposited on silicon dioxide (SiO2) and SiO2 substrates modified with self-assembled monolayers (SAMs) bearing octadecyl (C18), phenethyl, and aminopropyl functional groups. Atomic force microscopy revealed three-dimensional islands whose areal density and surface coverage are lowest on bare SiO2 substrates and highest on the neutral aromatic and aliphatic substrates. Increasing the pH of the solution from 8.2 to 10 dissociates catechol moieties in DM and inhibits adsorption on negatively charged SiO2 substrates. The growth rate of DM films on SAM-modified SiO2 is maximized at pH 9.5 and almost completely abolished at pH 10 because of increased DM solubility. The initial rates of DM adsorption were measured using quartz crystal microbalance with dissipation measurements. The initial adsorption rate is proportional to the nucleation density, which increases as the hydrophobicity of the substrate increases. Taken together, these data provide insight into the rates of heterogeneous nucleation and growth of DM on substrates with well-defined chemistries. [ABSTRACT FROM AUTHOR]

Adsorptionof 20 nm diameter silica nanoparticles grafted witha high density brush of the weak polymeric base poly(2-(dimethylamino)ethylmethacrylate) (SiO2-g-PDMAEMA) to thesilica/aqueous interface was investigated using ellipsometry and streamingpotential measurements. We measured SiO2-g-PDMAEMA adsorption to negatively charged silica surfaces in 1–100mM sodium chloride solutions in the pH range 5–10 to investigatethe role of electrostatics in the adsorption mechanism. In this systempH and ionic strength determine not only the charge density of thesilica adsorption substrate but also the degree of ionization andswelling of the PDMAEMA brushes on the nanoparticles, resulting innonmonotonic dependences of the extent of adsorption on pH and ionicstrength. SiO2-g-PDMAEMA displays significantlydifferent adsorption behavior from the linear PDMAEMA analogue, mostnotably in terms of a strongly hysteretic adsorption response to alteredpH and a greater tendency to adsorb under weak surface attractionconditions that prevail at high pH. [ABSTRACT FROM AUTHOR]

ABSTRACT A new unsymmetrical diamine, 2-(3-aminophenoxy)-6-(4-aminophenoxy)benzonitrile (3,4-APBN), is synthesized via two consecutive SNAr reactions and the temperature-dependent reactivity of the fluorides in 2,6-difluorobenzonitrile, whose first SNAr reaction occurs at 70 °C and second, at 100 °C, allowing timing control of reaction sequence and circumventing the transetherification side reaction. Thus, a series of polyimides (PIs) is prepared from the polymerization of 3,4-APBN with five common dianhydrides (6FDA, DSDA, OPDA, BTDA, and PMDA). For comparison, a second series is also prepared from two symmetrical diamines ([2,6-bis(3-aminophenoxy)benzonitrile (3,3-APBN) and 2,6-bis(4-aminophenoxy)benzonitrile (4,4-APBN)] and 6FDA or PMDA. The processability of the poly(amic acids) (PAAs), for the first series is greatly improved since their solution viscosities are much lower than PAAs based on symmetrical diamines. Besides having high glass-transition temperatures (249-332 °C), and thermal stability [5% weight loss in the range of 505-542 °C (air) and 512-546 °C (nitrogen)], these PIs form tough, transparent and flexible films that have a tensile-strength range of 82.1-121.3 MPa, elongations-at-break of 5.33-9.81%, and tensile moduli of 2.11-2.97 GPa. Their film dielectric constants are 3.08-3.62 at 10 kHz, moderately higher than that (2.92) of analogous PI (CP2) without nitrile groups. Overall, we found that the reduction of structural symmetry in repeat units can improve the polymer processibility as well as increasing their dielectric constants. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4998-5011 [ABSTRACT FROM AUTHOR]