Size-dependent nanoscale soldering of polystyrene colloidal crystals by supercritical fluids.

HYPOTHESIS: Polymer particles self-assembled into colloidal crystals have exciting applications in photonics, phononics, templates for nanolithography, and coatings. Cold soldering utilizing polymer plasticization by supercritical fluids enables a novel, low-cost, low-effort, chemical-free means for uniform mechanical strengthening of fragile polymer colloidal crystals at moderate temperatures. Here, we aim to elucidate the role of particle size and gas-specific response for the most efficient soldering, exploring the full potential of this method. EXPERIMENTS: We investigate the elastic properties of polystyrene colloidal crystals made of nanoparticles with different diameters (143 to 830 nm) upon treatment with supercritical Ar and He at room temperature. By employing Brillouin light scattering, we quantify the effect of nanoparticle size on the strengthening of interparticle contacts, evaluating the permanent change in the effective elastic modulus upon cold soldering. FINDINGS: The relative change in the effective elastic modulus reveals nonmonotonic dependence on the particle size with the most efficient soldering for mid-sized nanoparticles (about 610 nm diameter). We attribute this behavior to the crucial role of intrinsic fabrication impurities, which reduces the nanoparticles' free surface exposed to plasticization by supercritical fluids. Supercritical Ar, a good solvent for polystyrene, enabled effective soldering of nanoparticles, whereas high-pressure He treatment is entirely reversible.

Ordering kinetics of a tapered copolymer based on isoprene and styrene.

High molar mass copolymers with a tapered interface are mechanically tough materials with an accessible order-to-disorder transition temperature and hence processability. We report the first ordering kinetics for a tapered tetrablock copolymer in comparison to a conventional diblock copolymer made sequentially. We show that tapered copolymers belong to the Brazovskii "universality class," where fluctuations play a dominant role. Consequently, the order-to-disorder transition has a very weak, fluctuation-induced first-order character. The ordering kinetics of the lamellar phase from the supercooled disordered melt revealed several distinct differences associated with the range of metastability (increased), the timescales (bimodal), and the exact mechanism of ordering. The results are discussed in terms of the reduced interaction parameter and the introduction of structural defects within the lamellar grains.

Interactions between a responsive microgel monolayer and a rigid colloid: from soft to hard interfaces.

Responsive poly-N-isopropylacrylamide-based microgels are commonly used as model colloids with soft repulsive interactions. It has been shown that the microgel-microgel interaction in solution can be easily adjusted by varying the environmental parameters, e.g., temperature, pH, or salt concentration. Furthermore, microgels readily adsorb to liquid-gas and liquid-liquid interfaces forming responsive foams and emulsions that can be broken on-demand. In this work, we explore the interactions between microgel monolayers at the air-water interface and a hard colloid in the water. Force-distance curves between the monolayer and a silica particle were measured with the Monolayer Particle Interaction Apparatus. The measurements were conducted at different temperatures and lateral compressions, i.e., different surface pressures. The force-distance approach curves display long-range repulsive forces below the volume phase transition temperature of the microgels. Temperature and lateral compression reduce the stiffness of the monolayer. The adhesion increases with temperature and decreases with a lateral compression of the monolayer. When compressed laterally, the interactions between the microgels are hardly affected by temperature, as the directly adsorbed microgel fractions are nearly insensitive to temperature. In contrast, our findings show that the temperature-dependent swelling of the microgel fractions in the aqueous phase strongly influences the interaction with the probe. This is explained by a change in the microgel monolayer from a soft to a hard repulsive interface.

Interfacial Interactions During In Situ Polymer Imbibition in Nanopores.

Using in situ nanodielectric spectroscopy we demonstrate that the imbibition kinetics of cis-1,4-polyisoprene in native alumina nanopores proceeds in two time regimes both with higher effective viscosity than bulk. This finding is discussed by a microscopic picture that considers the competition from an increasing number of chains entering the pores and a decreasing number of fluctuating chain ends. The latter is a direct manifestation of increasing adsorption sites during flow. At the same time, the longest normal mode is somewhat longer than in bulk. This could reflect an increasing density of topological constraints of chains entering the pores with the longer loops formed by other chains.

Molecular Probe Diffusion in Thin Polymer Films: Evidence for a Layer with Enhanced Mobility Far above the Glass Temperature.

We studied experimentally the influence of interfaces on the dynamics in thin polymer films at temperatures far above the glass temperature (Tg + 80 °C). Polyisoprene (PI) was employed as a model system. We examined glass substrate supported films with thicknesses (d) spanning the range from 10 µm to 10 nm that correspond to d/Rg from 400 to 1, where Rg is the polymer radius of gyration. We employed fluorescence correlation spectroscopy (FCS) to monitor the translational diffusion of small fluorescent tracer molecules, dispersed at nanomolar concentrations in the PI matrix. In thick films, a single diffusion process correlated to the bulk segmental dynamics of the matrix polymer was present. However, when the film thickness was smaller than the normal dimension of the FCS observation volume, a second, faster diffusion process appeared, reflecting enhanced segmental dynamics near the free surface. Our results provide direct experimental evidence for the existence of a layer with enhanced mobility near the free surface of supported PI films at temperatures as high as 80 °C above the bulk Tg.

Phoxonic Hybrid Superlattice.

We studied experimentally and theoretically the direction-dependent elastic and electromagnetic wave propagation in a supported film of hybrid PMMA (poly[methyl-methacrylate])-TiO2 superlattice (SL). In the direction normal to the layers, this one-dimensional periodic structure opens propagation band gaps for both hypersonic (GHz) phonons and near-UV photons. The high mismatch of elastic and optical impedance results in a large dual phoxonic band gap. The presence of defects inherent to the spin-coating fabrication technique is sensitively manifested in the band gap region. Utilizing Brillouin light scattering, phonon propagation along the layers was observed to be distinctly different from propagation normal to them and can, under certain conditions (SL thickness and substrate elasticity), reveal the nanomechanical properties of the constituent layers. Besides the first realization of unidirectional phoxonic behavior, hybrid (soft-hard) periodic materials are a promising simple platform for opto-acoustic interactions and applications such as filters and Bragg mirrors.

Effect of the degree of dissociation of molecules in a monolayer at an air/water interface on the force between the monolayer and a like-charged particle in the subphase.

We used the monolayer particle interaction apparatus to measure the force between a monolayer of stearic acid or octadecanol at the air/water interface and a colloidal silica sphere. The silica sphere approached the monolayer from the aqueous subphase. The aim was to analyze how the magnitude of the charge of a deformable interface affects the interaction between that interface and a like-charged hard particle. The charge density of the stearic acid monolayer was controlled by adjusting the pH (5.8-9) and the surface pressure. The octadecanol monolayer acted as a reference; the alcohol headgroup did not dissociate between pH 5.8-9.0. Stable monolayers of dissociated stearic acid molecules were formed at the air/water interface by dissolving stearic acid into the subphase to give a saturated concentration at each pH value studied. The approach force curve showed that the electrostatic repulsion increased with an increasing degree of dissociation and therefore the charge of the monolayer. The strength of the repulsion corresponded to that measured between two like-charged hard surfaces, but the apparent range of the repulsion was larger for a deformable interface. Retracting force curves displayed a significant adhesion, whose magnitude and range depended on the surface pressure and subphase pH.

Fluorescence correlation spectroscopy directly monitors coalescence during nanoparticle preparation.

Dual color fluorescence cross-correlation spectroscopy (DC FCCS) experiments were conducted to study the coalescence and aggregation during the formation of nanoparticles. To assess the generality of the method, three completely different processes were selected to prepare the nanoparticles. Polymeric nanoparticles were formed either by solvent evaporation from emulsion nanodroplets of polymer solutions or by miniemulsion polymerization. Inorganic nanocapsules were formed by polycondensation of alkoxysilanes at the interface of nanodroplets. In all cases, DC FCCS provided fast and unambiguous information about the occurrence of coalescence and thus a deeper insight into the mechanism of nanoparticle formation. In particular, it was found that coalescence played a minor role for the emulsion-solvent evaporation process and the miniemulsion polymerization, whereas substantial coalescence was detected during the formation of the inorganic nanocapsules. These findings demonstrate that DC FCCS is a powerful tool for monitoring nanoparticles genesis.

A straightforward way to form close-packed TiO2 particle monolayers at an air/water interface.

The aim of this study was to analyze if and how monolayers of TiO(2) particles could be directly formed at the air/water interface and if these monolayers could be transferred to a solid surface. TiO(2) particles with diameters of 300 nm, 500 nm, 1 µm, 5 µm, 10 µm, and 20 µm formed stable monolayers at pH 2. At low surface pressures, the particles formed small two-dimensional aggregates. Particles up to a radius of 5 µm displayed close packing at increased surface pressures. Particles of 10 µm radius formed a loose network, which is attributed to the strong adhesion caused by the weight-induced lateral capillary attraction. Every monolayer of particles could be transformed to a solid surface by the Langmuir-Blodgett deposition. At pH 6 or 11, the particles did not form stable monolayers at the air/water interface. They were instead dispersed in the aqueous phase and eventually sank to the bottom of the trough. At pH 11 the monolayer could, however, be stabilized by the addition of salt (0.5 M NaCl). The results are interpreted based on a changed wettability of the particles depending on pH and salt concentration.

Tracer diffusion in silica inverse opals.

We employed fluorescence correlation spectroscopy (FCS) to study the diffusion of small fluorescence tracers in liquid filled silica inverse opals. The inverse opals consisted of a nanoporous silica scaffold spanning a hexagonal crystal of spherical voids of 360 nm diameter connected by circular pores of 70 nm diameter. The diffusion of Alexa Fluor 488 in water and of perylene-3,4,9,10-tetracarboxylic diimide (PDI) in toluene was studied. Three diffusion modes could be distinguished: (1) Free diffusion limited by the geometric constraints given by the inverse opal, where, as compared to the free solution, this diffusion is slowed down by a factor of 3-4, (2) slow diffusion inside the nanoporous matrix of the silica scaffold, and (3) diffusion limited by adsorption. On the length scale of the focus of a confocal microscope of roughly 400 nm diffusion was non-Fickian in all cases.

Adhesion forces in interactive mixtures for dry powder inhalers--evaluation of a new measuring method.

Dry powder inhalers mostly contain carrier based formulations where micronized drug particles are adhered to coarse carrier particles. The performance of the dry powder inhaler depends on the inhaler device, the inhalation manoeuvre and the formulation. The most important factor influencing the behaviour of the formulation is the adhesion force acting between the active ingredient and the carrier particles, which can be measured using different methods, for example the centrifuge technique or atomic force microscopy. In this study the tensile strength method, usually applied to determine cohesion forces between powder particles of one material, is optimized for adhesion force measurements between powder particles of unlike materials. Adhesion force measurements between the carrier materials lactose or mannitol and the drug substance salbutamol sulphate using the tensile strength method and the atomic force microscopy show higher values with increasing relative humidity. Consequently, the fine particle fraction determined using the Next Generation Impactor decreases with increasing relative humidity as a result of the enhanced interparticle interactions.