Sample cell for studying liquid interfaces with an in situ electric field using X-ray reflectivity and application to clay particles at oil-oil interfaces.

Commissioning results of a liquid sample cell for X-ray reflectivity studies with an in situ applied electrical field are presented. The cell consists of a Plexiglas container with lateral Kapton windows for air-liquid and liquid-liquid interface studies, and was constructed with grooves to accept plate electrodes on the walls parallel to the direction of the beam. Both copper and ITO plate electrodes have been used, the latter being useful for simultaneous optical studies. Commissioning tests were made at the I07 beamline of the Diamond Light Source.

Composite microdiscs with a magnetic belt: preparation, chaining properties, and use as switchable catalyst carriers.

We describe an emulsion-based preparation of patchy composite particles (diameter of 100-500 µm) consisting of a disclike epoxy core and a belt of porous polystyrene particles (diameter of 30 µm) with magnetite within the pores. Compared to the magnetically uniform polystyrene particles, the spontaneous aggregation of composite particles is suppressed when dispersed into liquid, which is attributed to the increased particle size, reduced magnetic susceptibility, and the shape of the magnetic domain distribution within the particles (spherical versus a belt). When the composite particles are coated by platinum-palladium layer we demonstrate they can be employed as switchable catalyst carriers, moving from one liquid phase to another when controlled by an external magnetic field.

Transparency enhancement for photoinitiated polymerization (UV curing) through magnetic field alignment in a piezoresistive metal/polymer composite.

We use a magnetic field to align nickel particles into stringlike assemblies in urethane oligomer mixtures and create a semitransparent UV-curable nickel particle/polymer composite with anisotropic electrical conductivity and piezoresistive properties. When the particles are uniformly distributed in the oligourethane matrix, the mixture is moderately conductive at higher particle fractions but becomes insulating once the fraction is below about 5 vol %. With the particle fraction below this threshold and using an external magnetic field, the particles are aligned into continuous pathways through the oligomer mixtures following the magnetic flux lines. The matrix is subsequently cured by UV light. This results in conductivity and piezoresistivity along the alignment direction, while the material is not conducting perpendicular to the alignment direction. The lower particle fraction results in a lower number of absorbers for UV light: the decrease from 5 to 1 vol % increases optical transmission from 10% to 50% in the UV/vis region. This leads to a shorter photocuring time, typically from tens of seconds to seconds for 300-µm-thick films at a wavelength of 365 nm. We propose that this concept could be applied in areas such as pressure sensors.

Oxygen-controlled phase segregation in poly(N-isopropylacrylamide)/laponite nanocomposite hydrogels.

The combination of nanoparticles and polymers into nanocomposite gels has been shown to be a promising route to creating soft materials with new or improved properties. In the present work, we have made use of Laponite nanoparticles in combination with a poly(N-isopropylacrylamide) (PNIPAAM) polymer and describe a phenomenon taking place during the polymerization and gelling of this system. The presence of small amounts of oxygen in the process induces two distinctly separated phases, one polymer-rich and one polymer-deficient water-clay phase. Complex interactions among clay, oxygen, and the polymer are found to govern the behavior of these phases. It is also observed that the initial clay concentration can be used to control the volume fraction of the polymer-deficient phase directly. The dynamics of the phase boundary is found to be dependent on water penetration and in general to exhibit non-Fickian behavior. An approach using video recording to monitor hydrogel swelling is also presented, and its advantages are addressed.

Conductivity enhancement in carbon nanocone adhesive by electric field induced formation of aligned assemblies.

We show how an alternating electric field can be used to assemble carbon nanocones (CNCs) and align these assemblies into microscopic wires in a commercial two-component adhesive. The wires form continuous pathways that may electrically connect the alignment electrodes, which leads to directional conductivity (∼10(-3) S/m) on a macroscopic scale. This procedure leads to conductivity enhancement of at least 2-3 orders of magnitude in the case where the CNC fraction (∼0.2 vol %) is 1 order of magnitude below the percolation threshold (∼2 vol %). The alignment and conductivity are maintained on curing that joins the alignment electrodes permanently together. If the aligned CNC wires are damaged before curing, they can be realigned by an extended alignment period. This concept has implications in areas such as electronic packaging technology.

Carbon nanocones: wall structure and morphology.

Large-scale production of conical carbon nanostructures is possible through pyrolysis of hydrocarbons in a plasma torch process. The resulting carbon cones occur in five distinctly different forms, and disc-shaped particles are produced as well. The structure and properties of these carbon cones and discs have been relatively little explored until now. Here we characterize the structure of these particles using transmission electron microscopy, synchrotron x-ray and electron diffraction. The carbon nanocones are found to exhibit several interesting structural features; instead of having a uniform cross-section, the walls consist of a relatively thin inner graphite-like layer with a non-crystalline envelope, where the amount of the latter can be modified significantly by annealing. The cones appear with a well-defined faceting along the cone edge, demonstrating strict long-range atomic ordering; they also present occasional examples of symmetry breaking, such as two apexes appearing in the same carbon nanocone.

Aggregation of magnetic holes in a rotating magnetic field.

We experimentally investigated field-induced aggregation of nonmagnetic particles confined in a magnetic fluid layer when rotating magnetic fields were applied. After application of a magnetic field rotating in the plane of the fluid layer, the single particles start to form two-dimensional clusters, like dimers, trimers, and more complex structures. These clusters aggregated again and again to form bigger clusters. During this nonequilibrium process, a broad range of cluster sizes was formed, and the scaling exponents z and z;{'} of the number of clusters N(t) approximately t;{-z;{'}} and average cluster size S(t) approximately t;{z} were calculated. The process could be characterized as diffusion-limited cluster-cluster aggregation. We found that all sizes of clusters that occurred during an experiment fall on a single curve, as the dynamic scaling theory predicts. However, the characteristic scaling exponents z;{'},z and crossover exponents Delta were not universal. A particle tracking method was used to find the dependence of the diffusion coefficients D_{s} on cluster size s . The cluster motions show features of Brownian motion. The average diffusion coefficients D_{s} depend on the cluster size s as a power law D_{s} proportional, variants;{gamma} where values of gamma as different as gamma=-0.62+/-0.19 and gamma=-2.08+/-0.51 were found in two of the experiments.

Memory of fluctuating Brownian dipolar chains.

Nonmagnetic particles in suspension in a ferrofluid act as magnetic holes when an external magnetic field is exerted: They acquire an effective dipolar moment opposing the surrounding one, which induces dipolar magnetic interactions. For a large enough imposed field and particle size, the induced interactions dominate the thermal forces, dipolar chains form. At equilibrium, these chains fluctuate under the effect of brownian noise. When the imposed magnetic field is suddenly decreased, these chains roughen dynamically. We study the time and size scaling of these fluctuations and roughening, and the relationships between the equilibrium and out of equilibrium behavior. We compare the experimental data both to Brownian dynamics simulations, and to a simple theory of semiflexible polymer chains, a generalization of the Rouse model. The scaling behavior of the experiments agree with the predictions of both theory and simulations over 5 orders of magnitudes. The roughening follows three successive regimes: The root mean square width of the chain initially evolves as W approximately t1/2, then it enters a subdiffusive regime where W approximately t1/4 and eventually it saturates to a level W approximately N, where N is the number of particles in the chain. The exact prefactors as a function of the applied field, particle diameter, and temperature are also derived analytically. We also show that this phenomenon can be described equivalently as a non-Markovian diffusion process for a particle in an environment with memory effects. Within this framework, our system is shown to confirm the predictions of theories for anomalous diffusion in systems with memory.

Physical properties of aqueous solutions of a thermo-responsive neutral copolymer and an anionic surfactant: turbidity and small-angle neutron scattering studies.

Aqueous mixtures of the anionic sodium dodecyl sulfate (SDS) surfactant and thermo-responsive poly(N-vinylcaprolactam) chains grafted with omega-methoxy poly(ethylene oxide) undecyl alpha-methacrylate (PVCL-g-C11EO42) have been characterized using turbidimetry and small-angle neutron scattering (SANS). Turbidity measurements show that the addition of SDS to a dilute aqueous copolymer solution (1.0 wt %) induces an increase of the cloud point (CP) value and a decrease of the turbidity at high temperatures. In parallel, SANS results show a decrease of both the average distance between chains and the global size of the objects in solution at high temperatures as the SDS concentration is increased. Combination of these findings reveals that the presence of SDS in the PVCL-g-C11EO42 solutions (1.0 wt %) promotes the formation of smaller aggregates and, consequently, leads to a more homogeneous distribution of the chains in solution upon heating of the mixtures. Moreover, the SANS data results show that the internal structure of the formed aggregates becomes more swollen as the SDS concentration increases. On the other hand, the addition of moderate amounts of SDS (up to 4 mm) to a semidilute copolymer solution (5.0 wt %) gives rise to a more pronounced aggregation as the temperature rises; turbidity and SANS studies reveal in this case a decrease of the CP value and an increase of the scattered intensity at low q. The overall picture that emerges from this study is that the degree of aggregation can be accurately tuned by varying parameters such as the temperature, level of surfactant addition, and polymer concentration.

Aggregation dynamics of nonmagnetic particles in a ferrofluid.

Nonmagnetic microspheres confined in a ferrofluid layer are denoted by magnetic holes. They form aggregates due to dipolar interactions when an external magnetic field is exerted. Their cluster-cluster aggregation was studied for various magnetic fields using optical microscopy, both for small spheres of diameters, d=1.9 and 4 microm, for which Brownian motion was important and for large spheres of diameter, d=14 microm, for which Brownian motion was not important. The results for the two smaller sizes were in agreement with standard dynamic scaling theory and the dynamic scaling exponent z for the average cluster length S(t) approximately t(z) was found to be slightly smaller than 0.5, while for the largest spheres the z exponent showed a strong dependence on the magnetic-field strength.

Dynamic roughening and fluctuations of dipolar chains.

Nonmagnetic particles in a carrier ferrofluid acquire an effective dipolar moment when placed in an external magnetic field. This fact leads them to form chains that will roughen due to Brownian motion when the magnetic field is decreased. We study this process through experiments, theory and simulations, three methods that agree on the scaling behavior over 5 orders of magnitude. The rms width goes initially as t(1/2), then as t(1/4) before it saturates. We show how these results complement existing results on polymer chains, and how the chain dynamics may be described by a recent non-Markovian formulation of anomalous diffusion.

Interaction model for magnetic holes in a ferrofluid layer.

Nonmagnetic spheres confined in a ferrofluid layer (magnetic holes) present dipolar interactions when an external magnetic field is exerted. The interaction potential of a microsphere pair is derived analytically, with precise care for the boundary conditions along the glass plates confining the system. Considering external fields consisting of a constant normal component and a high frequency rotating in-plane component, this interaction potential is averaged over time to exhibit the average interparticular forces acting when the imposed frequency exceeds the inverse of the viscous relaxation time of the system. The existence of an equilibrium configuration without contact between the particles is demonstrated for a whole range of exciting fields, and the equilibrium separation distance depending on the structure of the external field is established. The stability of the system under out-of-plane buckling is also studied. The dynamics of such a particle pair is simulated and validated by experiments.