Extracting microscopic insight from transient dielectric measurements during large amplitude oscillatory shear.

Probing the transient microstructure of soft matter far from equilibrium is an ongoing challenge to understanding material processing. In this work, we investigate inverse worm-like micelles undergoing large amplitude oscillatory shear using time-resolved dielectric spectroscopy. By controlling the Weissenburg number, we compare the non-linear microstructure response of branched and unbranched worm-like micelles and isolate distinct elastic effects that manifest near flow reversal. We validate our dielectric measurements with small angle neutron scattering and employ sequence of physical processes to disentangle the elastic and viscous contributions of the stress.

Fast Dynamics of Inverse Wormlike Micelles Probed Using Mechanical and Dielectric Spectroscopy.

The rheology of wormlike micelle (WLM) solutions is tunable by engineering the micellar structure and topology. While much is known about how microscopic properties influence the rheological characteristics, questions remain regarding the quantification of fast relaxation processes, including Rouse and rotational modes. These fast processes are challenging to access using mechanical spectroscopy as bending modes dominate high-frequency mechanical measurements. In this work, we demonstrate the use of dielectric spectroscopy (DES) to directly interrogate these fast relaxation modes in solutions containing reverse WLMs. These consist of lecithin solutions in n-decane swollen with water. We develop an equivalent circuit model that separates the fast spectral features from the low-frequency processes and show that this relaxation feature is consistent with a combination of high-frequency Rouse and rotational modes. Further, we show that the low-frequency response is not determined by polymer dynamics alone. These findings demonstrate the potential of DES measurements to describe WLM behavior and pave the way toward in situ measurements under steady and transient shear flow.

Branching and alignment in reverse worm-like micelles studied with simultaneous dielectric spectroscopy and RheoSANS.

Topology and branching play an important but poorly understood role in controlling the mechanical and flow properties of worm-like micelles (WLMs). To address the challenge of characterizing branching during flow of WLMs, dielectric spectroscopy, rheology, and small-angle neutron scattering (dielectric RheoSANS) experiments are performed simultaneously to measure the concurrent evolution of conductivity, permittivity, stress, and segmental anisotropy of reverse WLMs under steady-shear flow. Reverse WLMs are microemulsions comprised of the phospholipid surfactant lecithin dispersed in oil with water solubilized in the micelle core. Their electrical properties are independently sensitive to the WLM topology and dynamics. To isolate the effects of branching, dielectric RheoSANS is performed on WLMs in n-decane, which show fast breakage times and exhibit a continuous branching transition for water-to-surfactant ratios above the corresponding maximum in zero-shear viscosity. The unbranched WLMs in n-decane exhibit only subtle decreases in their electrical properties under flow that are driven by chain alignment and structural anisotropy in the plane perpendicular to the electric field and incident neutron beam. These results are in qualitative agreement with additional measurements on a purely linear WLM system in cyclohexane despite differences in breakage kinetics and a stronger tendency for the latter to shear band. In contrast, the branched micelles in n-decane (higher water content) undergo non-monotonic changes in permittivity and more pronounced decreases in conductivity under flow. The combined steady-shear electrical and microstructural measurements are capable, for the first time, of resolving branch breaking at low shear rates prior to alignment-driven anisotropy at higher shear rates.

Friction and adhesion control between adsorbed layers of polyelectrolyte brush-grafted nanoparticles via pH-triggered bridging interactions.

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.

Moringa oleifera Seed Protein Adsorption to Silica: Effects of Water Hardness, Fractionation, and Fatty Acid Extraction.

Motivated by the proposed use of cationic protein-modified sand for water filtration in developing nations, this study concerns the adsorption of Moringa oleifera seed proteins to silica surfaces. These proteins were prepared in model waters of varying hardness and underwent different levels of fractionation, including fatty acid extraction and cation exchange chromatography. Adsorption isotherms were measured by ellipsometry, and the zeta potentials of the resulting protein-decorated surfaces were measured by the rotating disk streaming potential method. The results indicate that the presence of fatty acids has little effect on the M. oleifera cationic protein adsorption isotherm. Adsorption from the unfractionated extract was indistinguishable from that of the cationic protein isolates at low concentrations but yielded significantly greater extents of adsorption at high concentrations. Adsorption isotherms for samples prepared in model hard and soft fresh waters were indistinguishable from each other over the measured bulk solution concentration range, but adsorption from hard or soft water was more extensive than adsorption from deionized water at moderate protein concentrations. Streaming potential measurements showed that adsorption reversed the net sign of the zeta potential of silica from negative to positive for all protein fractions and water hardness conditions at protein bulk concentrations as low as 0.03 µg/mL. This suggests that sands can be effectively modified with M. oleifera proteins using small amounts of seed extract under various local water hardness conditions. Finally, ellipsometry indicated that M. oleifera proteins adsorb irreversibly with respect to rinsing in these model fresh waters, suggesting that the modified sand would be stable on repeated use for water filtration. These studies may aid in the design of a simple, effective, and sustainable water purification device for developing nations.

Clustering and Percolation in Suspensions of Carbon Black.

High-structured carbon fillers are ubiquitous as the conductive additive comprising suspension-based electrochemical energy storage technologies. Carbon black networks provide the necessary electrical conductivity as well as mechanical percolation in the form of a yield stress. Despite their critical role in determining system performance, a full mechanistic understanding of the relationship between the electrical transport characteristics of the percolated, conductive networks of carbon black, and the rheological properties is lacking, which hinders the rational design and optimization of flowable electrodes and the processing of electrolytes for batteries. Here, we report on the microstructural origin of the rheological and electrical properties of two commonly used conductive additives in neat propylene carbonate. From quiescent mechanical and structural studies, we find that the gelation of these carbon black suspensions is best described by the dynamic arrest of a clustered fluid phase. In contrast, the temperature and frequency dependence of the ac conductivity near this transition shows that mesoscale charge transport is determined by hopping between localized states that does not require a stress-bearing network. This unique combination of microstructural characterization with rheological and electrical measurements enables testing prevailing theories of the connection between electrical and mechanical percolation as well as improving conductive additives to enhance electrochemical performance.

Sequential Adsorption of Nanoparticulate Polymer Brushes as a Strategy To Control Adhesion and Friction.

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.

Ionic Surfactant Binding to pH-Responsive Polyelectrolyte Brush-Grafted Nanoparticles in Suspension and on Charged Surfaces.

The interactions between silica nanoparticles grafted with a brush of cationic poly(2-(dimethylamino) ethyl methacrylate) (SiO2-g-PDMAEMA) and anionic surfactant sodium dodecyl sulfate (SDS) is investigated by dynamic light scattering, electrophoretic mobility, quartz crystal microbalance with dissipation, ellipsometry, and atomic force microscopy. SiO2-g-PDMAEMA exhibits pH-dependent charge and size properties which enable the SDS binding to be probed over a range of electrostatic conditions and brush conformations. SDS monomers bind irreversibly to SiO2-g-PDMAEMA at low surfactant concentrations (∼10(-4) M) while exhibiting a pH-dependent threshold above which cooperative, partially reversible SDS binding occurs. At pH 5, SDS binding induces collapse of the highly charged and swollen brush as observed in the bulk by DLS and on surfaces by QCM-D. Similar experiments at pH 9 suggest that SDS binds to the periphery of the weakly charged and deswollen brush and produces SiO2-g-PDMAEMA/SDS complexes with a net negative charge. SiO2-g-PDMAEMA brush collapse and charge neutralization is further confirmed by colloidal probe AFM measurements, where reduced electrosteric repulsions and bridging adhesion are attributed to effects of the bound SDS. Additionally, sequential adsorption schemes with SDS and SiO2-g-PDMAEMA are used to enhance deposition relative to SiO2-g-PDMAEMA direct adsorption on silica. This work shows that the polyelectrolyte brush configuration responds in a more dramatic fashion to SDS than to pH-induced changes in ionization, and this can be exploited to manipulate the structure of adsorbed layers and the corresponding forces of compression and friction between opposing surfaces.

Control of heterogeneous nucleation and growth kinetics of dopamine-melanin by altering substrate chemistry.

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.

Electrostatically controlled swelling and adsorption of polyelectrolyte brush-grafted nanoparticles to the solid/liquid interface.

Adsorption of 20 nm diameter silica nanoparticles grafted with a high density brush of the weak polymeric base poly(2-(dimethylamino)ethyl methacrylate) (SiO2-g-PDMAEMA) to the silica/aqueous interface was investigated using ellipsometry and streaming potential measurements. We measured SiO2-g-PDMAEMA adsorption to negatively charged silica surfaces in 1-100 mM sodium chloride solutions in the pH range 5-10 to investigate the role of electrostatics in the adsorption mechanism. In this system pH and ionic strength determine not only the charge density of the silica adsorption substrate but also the degree of ionization and swelling of the PDMAEMA brushes on the nanoparticles, resulting in nonmonotonic dependences of the extent of adsorption on pH and ionic strength. SiO2-g-PDMAEMA displays significantly different adsorption behavior from the linear PDMAEMA analogue, most notably in terms of a strongly hysteretic adsorption response to altered pH and a greater tendency to adsorb under weak surface attraction conditions that prevail at high pH.

Poly(ethylene oxide) star polymer adsorption at the silica/aqueous interface and displacement by linear poly(ethylene oxide).

Multiarm star copolymers with approximately 460 poly(ethylene oxide) (PEO) arms that have a degree of polymerization N = 45 were synthesized via atom transfer radical polymerization (ATRP) of PEO-methacrylate macromonomers in the presence of divinyl benzene cross-linkers. These are an example of molecular or nanoparticulate brushes that are of interest as steric stabilizers or boundary lubrication agents when adsorbed from solution to a solid/aqueous interface. We use ellipsometry to measure adsorption isotherms at the silica/aqueous interface for PEO star polymers and linear PEO chains having molecular weights comparable either to the star polymer or to the individual arms. The compactness of the PEO star polymers (molecular weight 1.2 × 10(6)) yields a saturation surface excess concentration that is approximately 3.5 times greater than that of the high molecular weight (1 × 10(6)) linear PEO. Adsorption of low molecular weight (6000) linear PEO was below the detection limit. Competitive adsorption experiments were conducted with ellipsometry, complemented by independent quartz crystal microbalance with dissipation (QCM-D) measurements. Linear PEO (high molecular weight) displaced preadsorbed PEO star polymers over the course of approximately 1.5 h, to form a mixed adsorbed layer having not only a significantly lower overall polymer surface excess concentration, but also a significantly greater amount of hydrodynamically entrapped water. Challenging a preadsorbed linear PEO (high molecular weight) layer with PEO star polymers produced no measurable change in the overall polymer surface excess concentration, but changes in the QCM-D energy dissipation and resonance frequency suggested that the introduction of PEO star polymers caused a slight swelling of the layer with a correspondingly small increase in entrapped water content.