We describe the self-assembly of nonspherical particles into crystals with novel structure and optical properties combining a partial photonic band gap with birefringence that can be modulated by an external field or quenched by solvent evaporation. Specifically, we study symmetric optical-scale polymer dumbbells with an aspect ratio of 1.58. Hard particles with this geometry have been predicted to crystallize in equilibrium at high concentrations. However, unlike spherical particles, which readily crystallize in the bulk, previous experiments have shown that these dumbbells crystallize only under strong confinement. Here, we demonstrate the use of an external electric field to align and assemble the dumbbells to make a birefringent suspension with structural color. When the electric field is turned off, the dumbbells rapidly lose their orientational order and the color and birefringence quickly go away. In this way, dumbbells combine the structural color of photonic crystals with the field addressability of liquid crystals. In addition, we find that if the solvent is removed in the presence of an electric field, the particles self-assemble into a novel, dense crystalline packing hundreds of particles thick. Analysis of the crystal structure indicates that the dumbbells have a packing fraction of 0.7862, higher than the densest known packings of spheres and ellipsoids. We perform numerical experiments to more generally demonstrate the importance of controlling the orientation of anisotropic particles during a concentration quench to achieve long-range order.
A method of simultaneous field‐ and flow‐directed assembly of anisotropic titania (TiO2) nanoparticle films from a colloidal suspension is presented. Titania particles are oriented by an alternating (ac) electric field as they simultaneously advect towards a drying front due to evaporation of the solvent. At high field frequencies (ν > ∼25 kHz) and field strengths (E > 300 V cm−1), the particles orient with their major axis along the field direction. As the front recedes, a uniform film with thicknesses of 1–10 µm is deposited on the substrate. The films exhibit a large birefringence (Δn ≈ 0.15) and high packing fraction (ϕ = 0.75 ± 0.08), due to the orientation of the particles. When the frequency is lowered, the particle orientation undergoes a parallel–random–perpendicular transition with respect to the field direction. The orientation dependence on field frequency and strength is explained by the polarizability of ellipsoidal particles using an interfacial polarization model. Particle orientation in the films also leads to anisotropic mechanical properties, which are manifested in their cracking patterns. In all, it is demonstrated that the field‐directed assembly of anisotropic particles provides a powerful means for tailoring nanoparticle film properties in situ during the deposition process.
Micrometer-sized polystyrene particles form two-dimensional crystals in alternating current (ac) electric fields. The induced dipole-dipole interaction is the dominant force that drives this assembly. We report measurements of forces between colloidal particles in ac electric fields using optical tweezers and find good agreement with the point dipole model. The magnitude of the pair interaction forces depends strongly on the bulk solution conductivity and decreases as the ionic strength increases. The forces also decrease with increasing field frequency. The salt and frequency dependences are consistent with double layer polarization with a characteristic relaxation frequency omega(CD) approximately a(2)/D, where a is the particle radius and D is the ion diffusivity. This enables us to reinterpret the order-disorder transition reported for micrometer-sized polystyrene particles [Lumsdon et al., Langmuir 20, 2108 (2004)], including the dependence on particle size, frequency, and ionic strength. These results provide a rational framework for identifying assembly conditions of colloidal particles in ac fields over a wide range of parameters.
Nanostructured thin films are fabricated by directing the assembly of anisotropic titanium dioxide particles from a colloidal suspension by fixed blade flow coating. The titania particles (equatorial radius a = 24 ± 4 nm, polar radius b = 130 ± 31 nm, aspect ratio b/a = 5.4 ± 0.9) undergo an isotropic-nematic (I-N) transition at a volume fraction ϕ* ≈ 0.40. For ϕ > ϕ* the deposited film has three structures depending on the substrate velocity, v. At a blade angle α = 25° and a gap d = 200 μm, nanoparticles orient either isotropically in the direction of the coating flow (v≥ 350 μm s(-1)), exhibit partially oriented "wavy" structures (100 < v < 300 μm s(-1)), or are isotropically oriented (v < 100 μm s(-1)). Below the I-N transition (ϕ < ϕ*), nanoparticles assemble into domains of uniform orientation with dimensions that increase with increasing v. Increasing the blade angle shifts these structural transitions to lower substrate velocities, consistent with an increasing extensional component of the flow. Established scaling relationships describe the film height dependence on ϕ and v. Overall, these results enable nanostructured films to be deposited with desired thickness and structure.
We study the transition of ordered structures to disordered bands and vortices in colloidal suspensions subjected to AC electric fields. We map the critical frequencies and field biases at which particles form disordered bands and vortices. These results are interpreted based on the trajectory dynamics of particle pairs using blinking optical tweezers. Under conditions that vortices are observed, individual particle pairs rotate out of alignment with the field. The direction and magnitude of these interactions determine the orientation and average angular velocity of the band revolution. Increasing the frequency of the electric field reduces the anomalous rotation of the particles pairs, consistent with the frequency dependence of the suspension order-to-disorder transition. This anomalous rotation is consistent with a torque on doublets generated by the mutual polarization of particles and phase lag of the induced dipoles.
A facile carbothermal route was adopted to obtain niobium carbide nanoparticles (NPs) embedded in carbon network from Nb2O5 to study photocatalytic behavior. Optimization of synthesis parameters to obtain single phase NbC NPs has been successfully done. The phase identification, morphology and nature of carbon were determined with the help of X-ray diffraction, transmission electron microscopy (TEM) and Raman spectroscopy. X-ray photoelectron spectroscopy (XPS) suggested the presence of multiple oxidation states of Nb associated to NbC and NbCxOy centers on the surface of NPs. Due to the presence of NbCxOy on the surface of NPs, absorption under visible region of EM spectrum has been observed by UV-visible spectroscopy. Different organic dyes (RhB, MB and MO) were used to study the effect of holding time on the photocatalytic performance of as-synthesized samples. RhB dye was found to be the most sensitive organic molecule among all the considered dyes and degraded 78% in 120 min.
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