Nematic-fluid structure in wall-field geometry. II. The direct correlation function

An explicit expression for the wall-nematic direct correlation function (DCF) is obtained for any orientation of the wall with respect to an external orienting field. It is found that inside the surface of the wall, the DCF rapidly tends to a function of the nematogen orientation and depends only on parameters of the bulk fluid. We suggest that the wall-nematic DCF can be used as an ansatz for the colloid-nematic DCF in dilute nematic colloids. The reliability of this ansatz is investigated at different field strengths in both isotropic and nematic regions. Our calculations for spherical colloidal particles show that this approximation is valid for colloidal particles that are large, but well within the physically realistic size range. The ansatz could also be applied to nonspherical colloidal particles.     

Parameters influencing the templated growth of colloidal crystals on chemically patterned surfaces

The influence of various experimental parameters on the vertical deposition and structure formation of colloidal crystals on chemically patterned surfaces, with hydrophilic and hydrophobic areas, was investigated. The pattern dimensions range from about 4 to 400 microm, which is much larger than the individual particle size (255 nm), to control the microscopic crystal shape rather than influencing the crystal lattice geometry (as achieved in colloidal epitaxy). The deposition resolution and selectivity were tested by varying the particle concentration in the suspension, the substrate withdrawing speed, pattern size and orientation, and wetting contrast between the hydrophilic and hydrophobic regions. The evolution of colloidal crystal thickness with respect to the pattern dimensions and deposition parameters was further studied. Our results show that the pattern size has a rather strong influence on the deposited number of colloid layers and on the crystal quality. Better results are obtained when the lines of a stripe pattern are oriented parallel to the withdrawing direction rather than perpendicular. The deposition resolution (defined as the minimum feature size on which particles can be deposited) depends on the wetting contrast and increases with lower average hydrophobicity of the substrate.     

Morphology of spinodal decompositions in liquid crystal-colloid mixtures

We study the morphology of spinodal decompositions (SDs) in mixtures of a liquid crystal and a colloidal particle by solving time-dependent Landau-Ginzburg equations for a conserved order parameter (concentration) and two nonconserved order parameters (orientation and crystallization). We numerically examine the coupling between concentration, nematic ordering, and crystalline ordering in two dimensional fluid mixtures, coexisting a nematic and a crystalline phase. On increasing the concentration of colloidal particles, we have three different SDs: a nematic order-induced SD, a phase-separation-induced SD (PSD), and a crystalline-order-induced SD (CSD). In NSD, the phase ordering can lead to fibrillar and cellular networks of the minority colloidal-particle-rich phase in early stages. In the PSD, we find a bicontinuous network structure consisting of a nematic phase rich in liquid crystal and a crystalline phase rich in colloidal particles. In the CSD, nematic droplets can be formed in a crystalline matrix. Asymmetric mixtures of a liquid crystal and a colloidal particle lead to rich varieties of morphologies.     

Colloidal lithographic nanopatterning via reactive ion etching

We report here a novel colloidal lithographic approach to the fabrication of nonspherical colloidal particle arrays with a long-range order by selective reactive ion etching (RIE) of multilayered spherical colloidal particles. First, layered colloidal crystals with different crystal structures (or orientations) were self-organized onto substrates. Then, during the RIE, the upper layer in the colloidal multilayer acted as a mask for the lower layer and the resulting anisotropic etching created nonspherical particle arrays and new patterns. The new patterns have shapes that are different from the original as a result of the relative shadowing of the RIE process by the top layer and the lower layers. The shape and size of the particles and patterns were dependent on the crystal orientation relative to the etchant flow, the number of colloidal layers, and the RIE conditions. The various colloidal patterns can be used as masks for two-dimensional (2-D) nanopatterns. In addition, the resulting nonspherical particles can be used as novel building blocks for colloidal photonic crystals.     

Amphiphilic azo polymer spheres, colloidal monolayers, and photoinduced chromophore orientation

In this work, azobenzene-containing colloidal spheres have been fabricated and used to construct photoresponsive monolayers. The colloidal spheres were prepared from an amphiphilic azobenzene-containing random copolymer through hydrophobic aggregation of the polymer chains, which was induced by adding the selective solvent (H2O) into a THF solution of the polymer. The size and size distribution of the spheres depended on the initial concentration of the azo polymer in THF and the H2O/THF ratio. Adjusting those factors and optimizing other preparation conditions, uniform colloidal spheres could be obtained. Monolayers composed of hexagonally close-packed colloidal spheres were prepared by the capillary-force-driven method. The colloidal monolayers showed obvious dichroism after laser irradiation due to the photoinduced azo-chromophore orientation occurred in the spheres. The orientation order parameter was related to the irradiation time and estimated to be 0.09 at the photostationary state. The colloidal spheres and their monolayers can potentially be used as building blocks or media for reversible optical data storage, photo-switching, sensors, and other photo-driven devices.     

Structural analysis of anisometric colloidal iron(III)-hydroxide particles and particle-aggregates incorporated in poly(vinyl-acetate) networks

Anisometrical colloidal iron(III)hydroxide particles and particle aggregates were incorporated in elastic poly(vinyl acetate) networks. A novel method has been developed to fix the colloidal structure of deformed samples. Digitalized image analysis has been applied in order to evaluate the micrographs. The rod-like particles allow for studying the local deformation and orientation due to uniaxial and triaxial deformations. The density correlation function as well as the micrographs show that the structure of aggregates is not influenced by the strain. Due to strong attractive interactions between the colloidal particles the developing strain is not enough to destroy the aggregate structure. The orientation behavior of the model filled networks can be satisfactorily described by using the affinity principle.     

Orientational Ordering of Dyes in the Glassy State of Liquid-Crystalline Side Group Polymers

Liquid-crystalline side group copolymers containing dyes can be macroscopic-ally oriented and the orientation can be locked-in below the glass transition temperature. The order parameters of anthraquinone dyes and a trisazo dye in nematic and smectic glasses were determined by optical absorption measurements. The dyes have higher degrees of order in the smectic glass than in the nematic glass. A comparison of order parameters of covalently bonded dyes with order parameters of monomeric dyes dissolved in the corresponding homopolymers demonstrates the influence of covalently anchoring the dye to the polymer.     

Active colloidal particles at fluid-fluid interfaces

This review explores the intersection between two important fields of colloid and interface science – that of active colloidal particles and of (passive) particles at fluid-fluid interfaces. The former uses energy input at the particle level to propel particle motions and direct dynamic assemblies. The latter relies on the spontaneous adsorption of particles at fluid interfaces to modify the interfacial energy, rheology, and permeability of biphasic materials. Here, we address two key questions that connect these otherwise distinct fields of study. How do liquid interfaces influence the dynamics of active or driven colloidal particles? How can particle activity influence the dynamics of liquid interfaces? These questions motivate the pursuit of active particle surfactants that move and organize at fluid interfaces to perform useful functions such as enhancing mass transport or modulating interfacial properties. Drawing examples from the literature, we discuss how fluid interfaces can provide a unique environment for the study of active colloids, how surface tension can be harnessed to propel particle motions, and how capillary interactions can be activated to achieve dynamically tunable emulsions and foams. We highlight opportunities for the future study and application of active particles at liquid interfaces.     

Orientational Ordering of Dyes in the Glassy State of Liquid-Crystalline Side Group Polymers

Abstract

Liquid-crystalline side group copolymers containing dyes can be macroscopic-ally oriented and the orientation can be locked-in below the glass transition temperature. The order parameters of anthraquinone dyes and a trisazo dye in nematic and smectic glasses were determined by optical absorption measurements. The dyes have higher degrees of order in the smectic glass than in the nematic glass. A comparison of order parameters of covalently bonded dyes with order parameters of monomeric dyes dissolved in the corresponding homopolymers demonstrates the influence of covalently anchoring the dye to the polymer.     

A model for methanol transport through Nafion membrane in diffusion cell

The transport of methanol through Nafion^® membrane in diffusion cell is investigated using the open circuit potential method at different initial methanol concentration solutions. A simple mathematical model based on quasi-steady-state diffusion for the transport of methanol across the membrane in a diffusion cell is developed to simulate the experimental data in order to measure the methanol permeability. The influence of the diffusion cell parameters and thickness of the membrane on the methanol permeability measurement has been evaluated and analyzed. By means of Maclaurin expansion technique, this model can be used to predict the deviation of methanol permeability determined by steady-state diffusion model.     

A Colloidal Au Monolayer Modulates the Conformation and Orientation of a Protein at the Electrode/Solution Interface

The orientation and conformation of adsorbed cytochrome c (cyt c) at the interface between an electrode modified with colloidal Au and a solution were studied by electrochemical, spectroscopic, and spectroelectrochemical techniques. The results indicate that the colloidal Au monolayer formed via preformation of an organic self‐assembled monolayer (SAM) can increase the electronic coupling between the SAM and cyt c in the same manner as bifunctional molecular bridges, one functional group of which is bound to the electrode surface while the other interacts with the protein surface. The approach of cyt c to the modified electrode/solution interface can be assisted by strong interactions of the intrinsic charge of colloidal particles with cyt c, while the heme pocket remains almost unchanged due to the screening effect of the negatively charged field created by the intrinsic charge. The conformational changes of cyt c induced by its adsorption at a bare glassy carbon electrode/solution interface and the effect of the electric field on the ligation state of the heme can be avoided at the colloidal‐Au‐modified electrode/solution interface. Finally, a possible model for the adsorption orientation of cyt c at the colloidal‐Au‐modified electrode/solution interface is proposed.     

A dielectric study on the relaxation and switching behaviour of liquid crystals confined within a colloidal network

The molecular ordering and dynamics of a liquid crystal (LC E7) in the presence of a three-dimensional network of submicron particles have been studied by dielectric relaxation spectroscopy. The field-dependent orientation of the LC was quantified by the director order parameter and modelled by use of a three-phase model. The influence of the colloidal network on the molecular dynamics was assessed from the dielectric spectra, e.g. from the position of relaxation peaks as well as from the strength of the two principal relaxations (α and γ). The spectra changed noticeably upon application of an increasing d.c. bias. A reduction of the threshold field was observed upon addition of colloidal particles to the LC. This was associated with a switching between two metastable states induced by anchoring on the filler particles. Modelled spectra were found to be in good agreement with the experimental data. The modelling showed that the confined LC phase is composed of two fractions, viz. an ordered and a disordered one with different molecular mobilities. Furthermore, switching experiments were conducted at various temperatures in order to evaluate the impact of the colloidal network on the (temperature-dependent) orientational behaviour of the LC molecules. For the colloid-filled LC higher conductivities were found, which gave rise to longer switch-off times.     

Effect of chlorine on adsorption/ultrafiltration treatment for removing natural organic matter in drinking water

In drinking water treatment, prechlorination is often applied in order to control microorganisms and taste-and-odor-causing materials, which may influence organics removal by adsorption and membrane filtration. Thus, the addition of chlorine into an advanced water treatment process using a hybrid of adsorption and ultrafiltration (UF) was investigated in terms of natural organic matter (NOM) removal and membrane permeability. A comparison between two adsorbents, iron oxide particles (IOP) and powdered activated carbon (PAC), was made to understand the sorption behavior for NOM with and without chlorination. Chlorine modified the properties of dissolved and colloidal NOM in raw water, which brought about lower TOC removal, during IOP/UF. The location of IOPs, whether they were in suspension or in a cake layer, affected NOM removal, depending on the presence of colloidal particles in feedwater. Chlorine also played a role in reducing the size of particulate matter in raw water, which could be in close association with a decline in permeate flux after chlorination.     

Direct visualization of colloidal rod assembly by confocal microscopy

The development of model materials and image processing methods to directly visualize and quantify colloidal rod assembly by means of confocal laser scanning microscopy (CLSM) is reported. Monodisperse fluorescent colloidal rods are prepared by the uniaxial extensional deformation of sterically stabilized microspheres at elevated temperatures. The particles are stably dispersed in refractive index matching mixed organic solvents for CLSM. An image processing algorithm is developed to detect rod backbones and extract particle centroids and orientation angles from the CLSM image volumes. By means of these methods we quantify the distribution of rod orientation angles in self-assembled structures of rods formed by sedimentation. We find the observations to be consistent with aspect-ratio-dependent jamming and orientational order/disorder transition in the rod sediments.     

General bottom-up construction of spherical particles by pulsed laser irradiation of colloidal nanoparticles: a case study on CuO

The development of a general method to fabricate spherical semiconductor and metal particles advances their promising electrical, optical, magnetic, plasmonic, thermoelectric, and optoelectric applications. Herein, by using CuO as an example, we systematically demonstrate a general bottom-up laser processing technique for the synthesis of submicrometer semiconductor and metal colloidal spheres, in which the unique selective pulsed heating assures the formation of spherical particles. Importantly, we can easily control the size and phase of resultant colloidal spheres by simply tuning the input laser fluence. The heating-melting-fusion mechanism is proposed to be responsible for the size evolution of the spherical particles. We have systematically investigated the influence of experimental parameters, including laser fluence, laser wavelength, laser irradiation time, dispersing liquid, and starting material concentration on the formation of colloidal spheres. We believe that this facile laser irradiation approach represents a major step not only for the fabrication of colloidal spheres but also in the practical application of laser processing for micro- and nanomaterial synthesis.     

Colloidal particles as elastic triads in nematic liquid crystals

ABSTRACT

In this short review we summarise already published results to manifest very important role of high order elastic terms in the formation of colloidal structures in nematic liquid crystals (NLC). We reveal that every colloidal particle in nematics can be effectively represented as a triad of nonzero elastic moments. Usually colloidal particles in NLCs are treated with their elastic dipole and/or quadrupole moments only. But we demonstrate that octupole, hexadecapole and even 64-pole moments play an important role as well and determine parameters of different 1D, 2D and even 3D colloidal crystals in NLCs. In general the triad of the first three nonzero elastic moments can describe almost all colloidal structures observed so far. Dipole particles should be considered as hard spheroids with a triad of the dipole, quadrupole and octupole moments. Quadrupole particles should be treated as hard spheres with a triad of quadrupole, hexadecapole and 64-pole elastic moments

PACS numbers: 61.30.Dk, 82.70.Dd, 64.70.M?     

X-Ray scattering study of ionic colloidal crystals

The scattering study of ionic colloidal crystals by using one- and two-dimensional ultra-small-angle scattering techniques is reviewed with a special reference to dilute dispersions. Because of large lattice constants of colloidal crystals, ultra-small angle regions need to be covered either by long distance optical systems combined with a synchrotron X-ray source or by adopting the Bonse–Hart optics. The crystal structure, lattice constant, and crystal orientation can be precisely determined.     

Particle arrays with patterned pores by nanomachining with colloidal masks

In summary, we have developed a new strategy for the fabrication of arrayed colloidal particles well-ordered nanometric holes of three or four fold symmetry by anisotropic reactive ion (plasma) etching of self-organized layers of colloidal spheres. We demonstrated that a mesoporous silica matrix with regular open windows could be used as a lithographic mask and the resulting arrangement of pores on a particle was dependent on the orientation of the colloidal particle stacking. A variety of organic and inorganic materials such as metals for metal-polymer composites, DNA and proteins, semiconducting and ceramic materials, and other polymers and small chemicals can be incorporated via chemical and physical attachment. Particles with patterned pores and composite particles by our nanomachining process can be used as novel functional materials in the field of electronics, photonics, and biotech areas.     

Sedimentation and electrophoresis of a porous floc and a colloidal particle coated with polyelectrolytes

Sedimentation and electrophoresis of porous colloid complex; a colloidal floc and a colloidal particle covered with adsorbed polyelectrolytes are visited to examine the characteristic length of the transport phenomena. In the sedimentation, the overall size of a floc is dominative in the determination of Stokes drag, while the permeability is determined by the largest pore in the floc. This picture is important when break-up of flocs in a turbulent flow is considered. When a colloidal particles is coated with polyelectrolytes, the characteristic length for diffusion is that of the diameter of colloidal particle plus protruding part of polymer chain adsorbed onto the particle. On the other hand, when the porous colloid complex is placed in the electric field, fluid surrounding the complex can easily penetrate into the complex by means of electro-osmosis. The diffusive part of electric double layer located inside of the complex is the source of strong driving force of this osmotic flow. Flow generated in this regime can be treated as a sort of shear driven. The characteristic length scale for transport phenomena is the Debye length or the distance between charged segments. These lengths are much shorter than the case of sedimentation and Brownian diffusion.