Charge Regulation at the Nanoscale as Evidenced from Light-Responsive Nanoemulsions.

Emulsions are indispensable in everyday life, and the demand for emulsions' diversity and control of properties is therefore substantial. As emulsions possess a high internal surface area, an understanding of the oil/water (o/w) interfaces at the molecular level is fundamental but often impaired by experimental limitations to probe emulsion interfaces in situ. Here, we have used light-responsive surfactants (butyl-AAP) that can photoisomerize between E and Z isomers by visible and UV light irradiation to tune the emulsion interfaces. This causes massive changes in the interface tension at the extended o/w interfaces in macroemulsions and a drastic shift in the surfactants' critical micelle concentration, which we show can be used to control both the stability and phase separation. Strikingly different from macroemulsions are nanoemulsions (RH ∼90 nm) as these are not susceptible to E/Z photoisomerization of the surfactants in terms of changes in their droplet size or ζ-potential. However, in situ second-harmonic scattering and pulsed-field gradient nuclear magnetic resonance (NMR) experiments show dramatic and reversible changes in the surface excess of surfactants at the nanoscopic interfaces. The apparent differences in ζ-potentials and surface excess provide evidence for a fixed charge to particle size ratio and the need for counterion condensation to renormalize the particle charge to a critical charge, which is markedly different compared to the behavior of very large particles in macroemulsions. Thus, our findings may have broader implications as the electrostatic stabilization of nanoparticles requires much lower surfactant concentrations, allowing for a more sustainable use of surfactants.

Dynamic molecular switches with hysteretic negative differential conductance emulating synaptic behaviour.

To realize molecular-scale electrical operations beyond the von Neumann bottleneck, new types of multifunctional switches are needed that mimic self-learning or neuromorphic computing by dynamically toggling between multiple operations that depend on their past. Here, we report a molecule that switches from high to low conductance states with massive negative memristive behaviour that depends on the drive speed and number of past switching events, with all the measurements fully modelled using atomistic and analytical models. This dynamic molecular switch emulates synaptic behavior and Pavlovian learning, all within a 2.4-nm-thick layer that is three orders of magnitude thinner than a neuronal synapse. The dynamic molecular switch provides all the fundamental logic gates necessary for deep learning because of its time-domain and voltage-dependent plasticity. The synapse-mimicking multifunctional dynamic molecular switch represents an adaptable molecular-scale hardware operable in solid-state devices, and opens a pathway to simplify dynamic complex electrical operations encoded within a single ultracompact component.

Photo-Responsive Control of Adsorption and Structure Formation at the Air-Water Interface with Arylazopyrazoles.

Smart interfaces that are responsive to external triggers such as light are of great interest for the development of responsive or adaptive materials and interfaces. Using alkyl-arylazopyrazole butyl sulfonate surfactants (alkyl-AAP) that can undergo E/Z photoisomerization when irradiated with green (E) and UV (Z) lights, we demonstrate through a combination of experiments and computer simulations that there can be surprisingly large changes in surface tension and in the molecular structure and order at air-water interfaces. Surface tensiometry, vibrational sum-frequency generation (SFG) spectroscopy, and neutron reflectometry (NR) are applied to the study of custom-synthesized AAP surfactants with octyl- and H-terminal groups at air-water interfaces as a function of their bulk concentration and E/Z configuration. Upon photoswitching, a drastic influence of the alkyl chain on both the surface activity and the responsiveness of interfacial surfactants is revealed from changes in the surface tension, γ, where the largest changes in γ are observed for octyl-AAP (Δγ ∼ 23 mN/m) in contrast to H-AAP with Δγ < 10 mN/m. Results from vibrational SFG spectroscopy and NR show that the interfacial composition and the molecular order of the surfactants drastically change with E/Z photoisomerization and surface coverage. Indeed, from analysis of the S-O (head group) and C-H vibrational bands (hydrophobic tail), a qualitative analysis of orientational and structural changes of interfacial AAP surfactants is provided. The experiments are complemented by resolution of thermodynamic parameters such as equilibrium constants from ultra-coarse-grained simulations, which also capture details like island formation and interaction parameters of interfacial molecules. Here, the interparticle interaction ("stickiness") and the interaction with the surface are adjusted, closely reflecting experimental conditions.

Influence of interfacial water and cations on the oxidation of CO at the platinum/ionic liquid interface.

CO oxidation is fundamental to the development of new catalyst materials for fuel cells and key for complete oxidation of small alcohols like methanol or ethanol on Pt catalysts. So far, room-temperature ionic liquids (RTIL) have been used to modify the selectivity and activity in electrocatalysis. In order to understand the mechanism of CO oxidation in RTIL in more detail we have investigated this reaction at the Pt(111)/1-butyl-3-methylimidazolium trifluorosulfonylimide [BMIM][NTf2] electrode/electrolyte interface as a function of H2O concentration and electrode potential with in situ sum-frequency generation (SFG) spectroscopy and infrared absorption spectroscopy (IRAS). Using SFG spectroscopy, we address the changes of linearly bonded CO molecules on Pt(111), while we monitor the changes in the bulk electrolyte with IRAS through vibrational bands from H2O, CO2 and CO. The presence of water in [BMIM][NTf2] shifts the onset potential for CO oxidation by more than 200 mV when the water concentration is increased from 0.01 to 1.5 M, which we relate to the incorporation and the availability of water at the electrode/electrolyte interface. The nature of the RTIL cation has also a large effect on the surface excess of H2O since RTILs like [BMMIM][NTf2] and [BMPyrr][NTf2] which are prone to form closed-packed structures, can block the incorporation of water and lead to more sluggish CO oxidation with larger overpotentials and oxidation in a much wider potential range for which we provide evidence by additional SFG measurements. These results clearly show that the choice of the RTIL is important for CO oxidation on Pt(111) electrode surfaces - an observation that is likely highly relevant also to other catalysts and catalytic reactions that require the presence of interfacial water.

Dynamic Wetting of Photoresponsive Arylazopyrazole Monolayers is Controlled by the Molecular Kinetics of the Monolayer.

Smart surfaces that can change their wettability on demand are interesting for applications such as self-cleaning surfaces or lab-on-a-chip devices. We have synthesized arylazopyrazole (AAP) phosphonic acids as a new class of photoswitchable molecules for functionalization of aluminum oxide surfaces. AAP monolayers were deposited on α-Al2O3(0001) and showed reversible E/Z photoswitching that can trigger contact angle changes of up to ∼10°. We monitored these changes on the macroscopic level by recording the contact angle while the monolayer was switched in situ. On the molecular level, time-dependent vibrational sum-frequency generation (SFG) spectroscopy provided information on the kinetic changes within the AAP monolayer and the characteristic times for E/Z switching. In addition, vibrational SFG at different relative humidity indicates that the thermal stability of the Z configuration is largely influenced by the presence of water which can stabilize the Z state and hinder E → Z switching of the AAP monolayer when it is wetted with H2O. Having established the switching times on the molecular scale, we additionally measured the dynamic contact angle and show that the time scales of the substrate and droplet dynamics can be extracted individually. For that, we report on a relaxation model that is solved analytically and is verified via a comparison with simulations of a Lennard-Jones system and with experimental data. The slower E to Z switching in the presence of the droplet as compared to the vapor phase is rationalized in terms of specific interactions of water with the exposed AAP moieties.

Adsorption of CTAB on Sapphire-c at High pH: Surface and Zeta Potential Measurements Combined with Sum-Frequency and Second-Harmonic Generation.

The adsorption of cetyltrimethylammonium bromide (CTA+Br-) on sapphire-c surfaces was studied at pH 10 below the surfactants' critical micelle concentration. The evolution of interfacial potentials as a function of CTAB concentration was characterized by surface and zeta potential measurements and complemented by molecular dynamic (MD) simulations as well as by second-harmonic (SHG) and vibrational sum-frequency generation (SFG) spectroscopy. The changes in interfacial potentials suggest that the negative interfacial charge due to deprotonated surface aluminols groups is neutralized and can be even overcompensated by the presence of CTA+ cations at the interface. However, SFG intensities from strongly hydrogen-bonded interfacial water molecules as well as SHG intensities decrease with both increasing CTAB concentration and the magnitude of the surface potential. They do not suggest a charge reversal at the interface, while the change in zeta potential is actually consistent with an apparent charge inversion. This can be qualitatively explained by results from MD simulation, which reveal adsorbed CTA+ cations outside a first strongly bound hydration layer of water molecules, where they can locally distort the structural order and replace some of the interfacial water molecules adjacent to the first layer. This is proposed to be the origin for the significant loss in SFG and SHG intensities with increasing CTAB concentration. Moreover, we propose that CTA+ can act as a counterion and enhance the occurrence of deprotonated surface aluminols that is consistent with the decrease in surface potential.

Surface Properties of Saponin-Chitosan Mixtures.

The surface properties of saponin and saponin-chitosan mixtures were analysed as a function of their bulk mixing ratio using vibrational sum-frequency generation (SFG), surface tensiometry and dilational rheology measurements. Our experiments show that saponin-chitosan mixtures present some remarkable properties, such as a strong amphiphilicity of the saponin and high dilational viscoelasticity. We believe this points to the presence of chitosan in the adsorption layer, despite its complete lack of surface activity. We explain this phenomenon by electrostatic interactions between the saponin as an anionic surfactant and chitosan as a polycation, leading to surface-active saponin-chitosan complexes and aggregates. Analysing the SFG intensity of the O-H stretching bands from interfacial water molecules, we found that in the case of pH 3.4 for a mixture consisting of 0.1 g/L saponin and 0.001 g/L chitosan, the adsorption layer was electrically neutral. This conclusion from SFG spectra is corroborated by results from surface tensiometry showing a significant reduction in surface tension and effects on the dilational surface elasticity strictly at saponin/chitosan ratios, where SFG spectra indicate zero net charge at the air-water interface.

Spiropyran Sulfonates for Photo- and pH-Responsive Air-Water Interfaces and Aqueous Foam.

Responsive foams and interfaces are interesting building blocks for active materials that respond and adapt to external stimuli. We have used the photochromic reaction of a spiropyran sulfonate surfactant to render interfacial, rising bubbles as well as foaming properties active to light stimuli. In order to address the air-water interface on a molecular level, we have applied sum-frequency generation (SFG) spectroscopy which has provided qualitative information on the surface excess and the interfacial charging state as a function of light irradiation and solution pH. Under blue light irradiation, the surfactant forms a closed ring spiro form (SP), whereas under dark conditions the ring opens and the merocyanine (MC) form is generated. Using SFG spectroscopy, we show that at the interface, different pH conditions of the bulk solution lead to changes in the interfacial charging state. We have exploited the fact that the MC surfactant's O-H group can be deprotonated as a function of pH and used that to tune the molecules net charge at the interface. In fact, SFG spectroscopy shows that with increasing pH the intensity of the O-H stretching band from interfacial water molecules increases, which we associate to an increase in surface net charge. At a pH of 5.3, irradiation with blue light leads to a reversible decrease of O-H intensities, whereas the C-H intensities were unchanged compared to the corresponding intensities under dark conditions. These results are indicative of changes in the surface net charge with light irradiation, which are also expected to influence the foam stability via changes in the electrostatic disjoining pressure. In fact, measurements of the foam stabilities are consistent with this hypothesis and show higher foam stability under dark conditions. At pH 2.7 this behavior is reversed as far as the surface tension and surface charging as well as the foam stability are concerned. This is corroborated by rising bubble experiments, which demonstrated an unprecedented reduction of ∼30% in bubble velocity when the bubbles were irradiated with blue light compared to the velocity of bubbles with the surfactants in the dark state. Clearly, the light-triggered changes can be used to control foams, rising bubbles, and fluid interfaces on a molecular level which renders them active to light stimuli.

Specific Ion Effects of Trivalent Cations on the Structure and Charging State of ß-Lactoglobulin Adsorption Layers.

The properties of proteins at interfaces are important to many processes as well as in soft matter materials such as aqueous foam. Particularly, the protein interfacial behavior is strongly linked to different factors like the solution pH or the presence of electrolytes. Here, the nature of the electrolyte ions can significantly modify the interfacial properties of proteins. Therefore, molecular level studies on interfacial structures and charging states are needed. In this work, we addressed the effects of Y3+ and Nd3+ cations on the adsorption of the whey protein ß-lactoglobulin (BLG) at air-water interfaces as the function of electrolyte concentration. Both cations caused very similar but dramatic changes at the interface and in the bulk solution. Here, measurements of the electrophoretic mobility and with vibrational sum-frequency generation (SFG) spectroscopy were applied and consistently showed a reversal of the BLG net charge at remarkably low ion concentrations of 30 (bulk) and 40 (interface) µM of Y3+ or Nd3+ for a BLG concentration of 15 µM. SFG spectra of carboxylate stretching vibrations from Asp or Glu residues of interfacial BLG showed significant changes in the resonance frequency, which we associate to specific and efficient binding of Y3+ or Nd3+ ions to the proteins carboxylate groups. Characteristic reentrant condensation for BLG moieties with bound trivalent ions was found in a broad concentration range around the point of zero net charge. The highest colloidal stability of BLG was found for ion concentrations <20 µM and >50 µM. Investigations on macroscopic foams from BLG solutions revealed the existence of structure-property relations between the interfacial charging state and the foam stability. In fact, a minimum in foam stability at 20 µM ion concentration was found when the interfacial net charge was negligible. At this concentration, we propose that the persistent BLG molecules and weakly charged BLG aggregates drive foam stability, while outside the bulk reentrant zone the electrostatic disjoining pressure inside foam lamellae dominates foam stability. Our results provide new information on the charge reversal at the liquid-gas interface of protein/ion dispersions. Therefore, we see our findings as an important step in the clarification of reentrant condensation effects at interfaces and their relevance to foam stability.

Hydroxypropyl cellulose as a green polymer for thermo-responsive aqueous foams.

Hydroxypropyl cellulose (HPC) is a surface active polymer that can change its solubility as a function of temperature. This makes HPC interesting for responsive foams, where macroscopic properties need to be reversibly changed on demand. Analysis of aqueous HPC foams as a function of temperature showed a moderate decrease in foam half-life time from 9000 to 4000 s, when the temperature was increased. However, within a narrow temperature range of ±2 °C a dramatic decrease in half-life time to <120 s was observed at 43 °C in the absence and at 31 °C in the presence of 0.7 M NaCl. These drastic changes are highly reversible and are associated to the lower critical solution temperatures (LCST) of HPC in aqueous solutions. In fact, dynamic light scattering experiments indicate that HPC molecules form aggregates at temperatures >31 °C (0.7 M NaCl) and >43 °C (0 M NaCl), which shrink in size when the temperature is increased further. From these results, we conclude that the LCST of 1 MDa HPC is at 43 °C when no salt is present and is at 31 °C in aqueous solutions with 0.7 M NaCl. In addition, shear rheology of bulk solutions and surface tensiometry indicate that the solution's viscosity and the surface pressure dramatically change at the respective LCSTs. Obviously, the solvent's viscosity triggers substantial changes in foam drainage at the LCST, which is shown to be the main driving force for the temperature responsiveness of HPC foams.

CnTAB/polystyrene sulfonate mixtures at air-water interfaces: effects of alkyl chain length on surface activity and charging state.

Binding and phase behavior of oppositely charged polyelectrolytes and surfactants with different chain lengths were studied in aqueous bulk solutions and at air-water interfaces. In particular, we have investigated the polyanion poly(sodium 4-styrenesulfonate) (NaPSS) and the cationic surfactants dodecyltrimethylammonium bromide (C12TAB), tetradecyltrimethylammonium bromide (C14TAB) and cetyltrimethylammonium bromide (C16TAB). In order to reveal the surfactant/polyelectrolyte binding, aggregation and phase separation of the mixtures, we have varied the NaPSS concentration systematically and have kept the surfactant concentration fixed at 1/6 of the respective critical micelle concentration. Information on the behavior in the bulk solution was gained by electrophoretic mobility and turbidity measurements, while the surface properties were studied using surface tension measurements and vibrational sum-frequency generation (SFG). This has enabled us to relate bulk to interfacial properties with respect to the charging state and the surfactants' binding efficiency. We found that the latter two are strongly dependent on the alkyl chain length of the surfactant and that binding is much more efficient as the alkyl chain length of the surfactant increases. This also results in a different phase behavior as shown by turbidity measurements of the bulk solutions. Charge neutral aggregates that are forming in the bulk adsorb onto the air-water interface - an effect that is likely caused by the increased hydrophobicity of CnTAB/PSS complexes. This conclusion is corroborated by SFG spectroscopy, where we observe a decrease in the intensity of O-H stretching bands, which is indicative of a decrease in surface charging and the formation of interfaces with negligible net charge. Particularly at mixing ratios that are in the equilibrium two-phase region, we observe weak O-H intensities and thus surface charging.

Specific Ion Effects of Dodecyl Sulfate Surfactants with Alkali Ions at the Air-Water Interface.

The influence of Li+, Na+ and Cs+ cations on the surface excess and structure of dodecyl sulfate (DS-) anions at the air-water interface was investigated with the vibrational sum-frequency generation (SFG) and surface tensiometry. Particularly, we have addressed the change in amplitude and frequency of the symmetric S-O stretching vibrations as a function of electrolyte and DS- concentration in the presence of Li+, Na+ and Cs+ cations. For the Li+ and Na+ ions, we show that the resonance frequency is shifted noticeably from 1055 cm-1 to 1063 cm-1 as a function of the surfactants' surfaces excess, which we attribute to the vibrational Stark effect within the static electric field at the air-water interface. For Cs+ ions the resonance frequency is independent of the surfactant concentration with the S-O stretching band centered at 1063 cm-1. This frequency is identical to the frequency at the maximum surface excess when Li+ and Na+ ions are present and points to the ion pair formation between the sulfate headgroup and Cs+ counterions, which reduces the local electric field. In addition, SFG experiments of the O-H stretching bands of interfacial H2O molecules are used in order to calculate the apparent double layer potential and the degree of dissociation between the surfactant head group and the investigated cations. The latter was found to be 12.0%, 10.4% and 7.7% for lithium dodecyl sulfate (LiDS), sodium dodecyl sulfate (SDS) and cesium dodecyl sulfate (CsDS) surfactants, which is in agreement with Collins 'rule of matching water affinities'.

Effects of Ca2+ Ion Condensation on the Molecular Structure of Polystyrene Sulfonate at Air-Water Interfaces.

The structure of poly(sodium 4-styrenesulfonate) (NaPSS) polyelectrolytes at air-water interfaces was investigated with tensiometry, ellipsometry, and vibrational sum-frequency generation (SFG) in the presence of low and high CaCl2 concentrations. In addition, we have studied the foaming behavior of 20 mM NaPSS solutions to relate the PSS molecular structure at air-water interfaces to foam properties. PSS polyelectrolytes without additional salt exhibited significant surface activity, which can be tuned further by additions of CaCl2. The hydrophobicity of the backbone due to incomplete sulfonation during synthesis is one origin, whereas the effective charge of the polyelectrolyte chain is shown to play another major role. At low salt concentrations, we propose that the polyelectrolyte is forming a layered structure. The hydrophobic parts are likely to be located directly at the interface in loops, whereas the hydrophilic parts are at low concentrations stretched out into near-interface regions in tails. Increasing the Ca2+ concentration leads to ion condensation, a collapse of the tails, and likely to Ca2+ intra- and intermolecular bridges between polyelectrolytes at the interface. The increase in both surface excess and foam stability originates from changes in the polyelectrolyte's hydrophobicity due to Ca2+ condensation onto the PSS polyanions. Consequently, charge screening at the interface is enhanced and repulsive electrostatic interactions are reduced. Furthermore, SFG spectra of O-H stretching bands reveal a decrease in intensity of the low-frequency branch when c(Ca2+) is increased whereas the high-frequency branch of O-H stretching modes persists even for 1 M CaCl2. This originates from the remaining net charge of the PSS polyanions at the air-water interface that is not fully compensated by condensation of Ca2+ ions and leads to electric-field-induced contributions to the SFG spectra of interfacial H2O. A charge reversal of the PSS net charge at the air-water interface is not observed and is consistent with bulk electrophoretic mobility measurements.

Smart Air-Water Interfaces with Arylazopyrazole Surfactants and Their Role in Photoresponsive Aqueous Foam.

A new light-switchable azo-surfactant arylazopyrazole tetraethylene glycol carboxylic acid (AAP-E4) was used as a molecular building block to functionalize macroscopic foams. AAP-E4 was studied in the bulk solution with UV/vis spectroscopy and at the interface with sum-frequency generation (SFG) as well as tensiometry. Additional foaming experiments were performed with a dynamic foam analyzer to study the role of AAP-E4 surfactants at the ubiquitous air-water interface as well as within macroscopic foam. In the bulk, it is possible to switch the AAP-E4 surfactant reversibly from trans to cis configurations and vice versa using 380 nm UV and 520 nm green light, respectively. At the interface, we demonstrate the excellent switching ability of AAP-E4 surfactants and a substantial modification of the surface tension. In addition, we show that the response of the interface is strongly influenced by lateral electrostatic interactions, which can be tuned by the charging state of AAP-E4. Consequently, the electrostatic disjoining pressure and thus the foam stability are highly dependent on the bulk pH and the charging state of the interface. For that reason, we have studied both the surface net charge (SFG) and the surface excess (tensiometry) as important parameters that determine foam stability in this system and show that neutral pH conditions lead to the optimal compromise between switching ability, surface excess, and surface charging. Measurements on the foam stability demonstrated that foams under irradiation with green light are more stable than foams irradiated with UV light.

Molecular structure of octadecylphosphonic acids during their self-assembly on α-Al2O3(0001).

The formation of octadecylphosphonic acid (ODPA) self-assembled monolayers (SAMs) from 2-propanol solutions on hydroxylated α-Al2O3(0001) surfaces was studied in situ and in real time at the solid/liquid interface. Time-resolved vibrational spectra from sum-frequency generation (SFG) of C-H stretching modes revealed contributions from ODPA's alkyl backbone and the terminal methyl group as well as vibrational bands that originated from the presence of 2-propanol molecules at the α-Al2O3 surface. 2-Propanol signatures in SFG spectra decreased during SAM formation. This is due to adsorption of ODPA molecules which trigger desorption of 2-propanol from the α-Al2O3(0001) surface, so that these sites can be occupied by ODPA molecules. SAM formation was studied for different bulk concentrations of ODPA which changed substantially both the quality and the coverage of the final SAM. At initial stages of SAM growth, SFG spectra are dominated by methylene contributions and are indicative for a low molecular order and coverage of ODPA molecules. For concentrations of ODPA ≤2 mM this situation did not change within reasonable adsorption times (∼16 h) while for 5 and 30 mM concentrations a dramatic increase in molecular order and coverage within the first 2 h of adsorption is observed. Thermodynamic analysis using Langmuir adsorption kinetics provided equilibrium constants and the Gibbs free energy of adsorption between -24 and -28 kJ mol-1.

Structure of Polystyrenesulfonate/Surfactant Mixtures at Air-Water Interfaces and Their Role as Building Blocks for Macroscopic Foam.

Air/water interfaces were modified by oppositely charged poly(sodium 4-styrenesulfonate) (NaPSS) and hexadecyltrimethylammonium bromide (CTAB) polyelectrolyte/surfactant mixtures and were studied on a molecular level with vibrational sum-frequency generation (SFG), tensiometry, surface dilatational rheology and ellipsometry. In order to deduce structure property relations, our results on the interfacial molecular structure and lateral interactions of PSS-/CTA+ complexes were compared to the stability and structure of macroscopic foam as well as to bulk properties. For that, the CTAB concentration was fixed to 0.1 mM, while the NaPSS concentration was varied. At NaPSS monomer concentrations <0.1 mM, PSS-/CTA+ complexes start to replace free CTA+ surfactants at the interface and thus reduce the interfacial electric field in the process. This causes the O-H bands from interfacial H2O molecules in our SFG spectra to decrease substantially, which reach a local minimum in intensity close to equimolar concentrations. Once electrostatic repulsion is fully screened at the interface, hydrophobic PSS-/CTA+ complexes dominate and tend to aggregate at the interface and in the bulk solution. As a consequence, adsorbate layers with the highest film thickness, surface pressure, and dilatational elasticity are formed. These surface layers provide much higher stabilities and foamabilities of polyhedral macroscopic foams. Mixtures around this concentration show precipitation after a few days, while their surfaces to air are in a local equilibrium state. Concentrations >0.1 mM result in a significant decrease in surface pressure and a complete loss in foamability. However, SFG and surface dilatational rheology provide strong evidence for the existence of PSS-/CTA+ complexes at the interface. At polyelectrolyte concentrations >10 mM, air-water interfaces are dominated by an excess of free PSS- polyelectrolytes and small amounts of PSS-/CTA+ complexes which, however, provide higher foam stabilities compared to CTAB free foams. The foam structure undergoes a transition from wet to polyhedral foams during the collapse.

Interaction between Polymeric Additives and Secondary Fluids in Capillary Suspensions.

Capillary suspensions are ternary systems including a solid and two liquid phases representing a novel formulation platform for pastes with unique processing and end-use properties. Here we have investigated aqueous suspensions of non-Brownian graphite particles including different polymers commonly used as thickening agents or binders in paste formulations. We have studied the interaction between these additives and organic solvents in order to elucidate its effect on the characteristic formation of a particle network structure in corresponding ternary capillary suspension systems. Organic solvents with different polarity have been employed, and in the presence of nonadsorbing poly(ethylene oxide), all of them, whether they preferentially wet the graphite surface or not, induce the formation of a network structure within the suspension as indicated by a strong change in rheological properties. However, when the adsorbing polymers carboxymethylcellulose and poly(vinylpyrrolidone) are included, the drastic change in rheological behavior occurs only when polar organic solvents are used as secondary liquids. Obviously, these solvents can form pendular bridges, finally resulting in a sample-spanning particle network. Vibrational sum frequency spectroscopy provides evidence that these polar liquids remove the adsorbed polymer from the graphite particles. In contrast, nonpolar and nonwetting solvents do not force polymer desorption. In these cases, the formation of a percolating network structure within the suspensions is presumably prevented by the strong steric repulsion among graphite particles, not allowing for the formation of particle clusters encapsulating the secondary liquid. Accordingly, polymeric additives and secondary fluids have to be carefully selected in capillary suspension formulations, then offering a new pathway to customize paste formulations. The polymer may serve to adjust an appropriate viscosity level, and the capillary bridging induces the desired degree of shear thinning. Alternatively, the polymer may be selected with respect to its binding properties in the final dry product, and capillary bridging may be used to control the flow and processing behavior of the wet paste.

Lubrication of Individual Microcontacts by a Self-Assembled Alkyl Phosphonic Acid Monolayer on α-Al2O3(0001).

We report on the tribological behavior of a self-assembled alkyl phosphonic acid monolayer on the microscale using the colloidal probe technique. Friction-load data and adhesion forces were measured with borosilicate glass particles on uncoated and octadecylphosphonic acid (ODPA) coated α-Al2O3(0001) surfaces. A significant decrease in friction force was observed after surface coating, while the adhesion force was only moderately reduced. We assume the lubrication effect of the ODPA self-assembled monolayer (SAM) to be close to the maximum obtainable of alkyl phosphonic acids in the studied system due to the high molecular order which was confirmed by vibrational sum-frequency generation. At small loads, a nonlinear dependence of friction force to load was maintained after surface coating. However, a shift from a contact behavior well described by the DMT model toward the JKR model occurred that is possibly related to the altered elastic properties of the coated surface. With increasing load, a linear friction-load behavior was observed on the coated samples. Molecular plowing and adhesive interactions were identified as responsible mechanisms. In all friction experiments, we could not detect any wear neither of the colloidal probes nor at the surfaces of uncoated and coated samples. This proves the high wear resistivity of the studied ODPA SAM.

Specific effects of Ca(2+) ions and molecular structure of ß-lactoglobulin interfacial layers that drive macroscopic foam stability.

ß-Lactoglobulin (BLG) adsorption layers at air-water interfaces were studied in situ with vibrational sum-frequency generation (SFG), tensiometry, surface dilatational rheology and ellipsometry as a function of bulk Ca(2+) concentration. The relation between the interfacial molecular structure of adsorbed BLG and the interactions with the supporting electrolyte is additionally addressed on higher length scales along the foam hierarchy - from the ubiquitous air-water interface through thin foam films to macroscopic foam. For concentrations <1 mM, a strong decrease in SFG intensity from O-H stretching bands and a slight increase in layer thickness and surface pressure are observed. A further increase in Ca(2+) concentrations above 1 mM causes an apparent change in the polarity of aromatic C-H stretching vibrations from interfacial BLG which we associate to a charge reversal at the interface. Foam film measurements show formation of common black films at Ca(2+) concentrations above 1 mM due to considerable decrease of the stabilizing electrostatic disjoining pressure. These observations also correlate with a minimum in macroscopic foam stability. For concentrations >30 mM Ca(2+), micrographs of foam films show clear signatures of aggregates which tend to increase the stability of foam films. Here, the interfacial layers have a higher surface dilatational elasticity. In fact, macroscopic foams formed from BLG dilutions with high Ca(2+) concentrations where aggregates and interfacial layers with higher elasticity are found, showed the highest stability with much smaller bubble sizes.

Self-Assembled Monolayers Get Their Final Finish via a Quasi-Langmuir-Blodgett Transfer.

The growth of self-assembled monolayers (SAMs) of octadecylphosphonic acid (ODPA) molecules on α-Al2O3(0001) and subsequent dewetting of the SAMs were studied with a combination of in situ sum-frequency generation (SFG) and molecular dynamics (MD) simulations. Although SAM growth after deposition times >8 h reduces to nearly negligible values, the resultant ODPA SAMs in solution are still not in a well-ordered state with the alkyl chains in all-trans configurations. In fact, in situ SFG spectroscopy revealed a comparatively high concentration of gauche defects of the SAM in the ODPA 2-propanol solution even after a growth time of 16 h. Here, results of the MD simulations strongly suggest that defects can be caused by ODPA molecules which are not attached to the substrate but are incorporated into the SAM layer with the polar headgroup oriented into the 2-propanol solvent. This inverted adsorption geometry of additional ODPA molecules blocks adsorption sites and thus stabilizes the SAM without improving ordering to an extent that all molecules are in the all-trans configuration. While persistent in solution, the observed defects can be healed out when the SAMs are transferred from the solvent to a gas phase. During this process, a quasi-Langmuir-Blodgett transfer of molecules takes place which drives the SAM into a higher conformational state and significantly improves its quality.