Dynamics of interacting Brownian particles in concentrated colloidal suspensions

We are concerned with dynamic properties of interacting Brownian particles in concentrated colloidal suspensions. An effective diffusion coefficient measured by the modulated in phase low-coherence dynamic light scattering technique is investigated as a function of the volume fraction. The experimental results are compared with the numerical ones calculated under both the Cohen-de Schepper approximation for hydrodynamic interaction and the Percus-Yevick approximations for structural effect. It is confirmed that the Brownian motion of particles in the range of volume fraction from 0.01 to 0.2 is mainly dominated by the hydrodynamic interaction rather than the structural effect, which can be described well by the Cohen-de Schepper approximation.     

SiO2 nanoparticles surface modified with polyethyleneimine-oleic acid complex as stabilizers of Ni fine particles in dense nonaqueous suspensions

SiO₂ nanoparticles (NPs) surface modified with polyethyleneimine-oleic acid complex (PEI-OA) has successfully prepared in a simple manner as a stabilizer of metal (Ni) fine particles (FPs) as well as a component of Ni/SiO₂ composite particles. Starting from SiO₂ NPs which were collected through centrifugation of commercial SiO₂ colloids, it was found that PEI-OA can effectively adsorbed on collected SiO₂ NPs surface during their redispersion process in toluene with the assistance of ultrasonication. The aggregated particle size (Z-average size) in toluene could be successfully reduced to c.a. 100 nm under saturated adsorption of PEI-OA. It was also found that PEI-OA-modified SiO₂ NPs can effectively attach to the Ni FPs by a simple mixing process in toluene. The FE-SEM observation confirmed the adsorption of the PEI-OA-modified SiO₂ NPs on the Ni FPs without forming severe NP aggregates. Owing to the attachment of the PEI-OA-modified SiO₂ NPs with surfaces that are compatible to toluene and α-terpineol, the suspension stability of the Ni/SiO₂ composite particles in these solvents drastically improved. The result was confirmed by the effective reduction of the sedimentation velocity of diluted suspensions as well as by the reduction of the viscosity of dense suspensions.     

Effect of polyethyleneimine-fatty acid complex type dispersant structure on the overall processing chain of Si3N4 ceramics using multicomponent non-aqueous slurries

The effect of fatty acid structure of polyethyleneimine (PEI)-fatty acid complex, which was designed as a polymer dispersant for multi-component non-aqueous slurries, on the overall processing chain of Si₃N₄ ceramics involving slurry stabilization, spray drying, compaction, and liquid sintering was investigated using PEI-oleic acid (PEI-OA) and PEI-isostearic (PEI-ISA) complexes. Si₃N₄-Y₂O₃-Al₂O₃-AlN-TiO₂/toluene slurries were selected as a real model for Si₃N₄-based multicomponent slurries. It was observed that both PEI-OA and PEI-ISA can stabilize Si₃N₄-Y₂O₃-Al₂O₃-AlN-TiO₂/toluene slurries; however, the PEI-ISA system tended to have slightly higher slurry viscosity, which was suspected to be due to the interactions between protruded PEI segments among short ISA chains. The spray-dried granules from PEI-ISA-stabilized slurry were observed to have filled structures with higher surface roughness whereas those prepared from PEI-OA-stabilized slurry were observed to have hollow-structured granules. The granules prepared from PEI-OA slurry had improved flow and compaction properties with higher relative density of green compacts compared with those prepared from PEI-ISA-stabilized slurry, whereas the relative density and microstructural homogeneity of S₃N₄ ceramics sintered at 1600?°C for 2?h were observed to be higher for the PEI-ISA system. It is suspected that PEI-OA effectively improved the dispersion stability of multicomponent slurries and flow/compaction properties of granules; however, the inhomogeneous microstructures of green compacts induced by the hollow-structured granules had an adverse effect on the sintering of Si₃N₄ ceramics.     

Preparation and encapsulation of white/yellow dual colored suspensions for electrophoretic displays

C.I. Pigment Yellow 181 (PY181) composite particles encapsulated by polyethylene (PE) were prepared by dispersion polymerization method, and C.I. Pigment Yellow 110 (PY110) composite particles encapsulated by polystyrene (PS) with mini-emulsion polymerization method were achieved, respectively. The modified pigments were characterized by fourier transform infrared spectroscopy, scanning electron microscope and transmission electron microscope. Compared with the PE-coated PY 181 pigments, the PS-coated PY-110 particles had a narrow particle size distribution, regular spherical and average particle size of 450 nm. Suspension 1 and suspension 3 were prepared by the two composite particles dispersed in isopar M. A chromatic electrophoretic display cell consisting of yellow particles was successfully fabricated using dispersions of yellow ink particles in a mixed dielectric solvent with white particles as contrast. The response behavior and the contrast ratio to the electric voltage were also examined. The contrast ratio of pigments modified by polystyrene was 1.48, as well as the response time was 2 s, which were better than those of pigments modified by polyethylene.     

Synthesis of polystyrene@silica particles through soap-free emulsion polymerization and sol-gel reaction on polymer surfaces

Polystyrene@silica particles were produced through soap-free emulsion polymerization (SFEP) of styrene and N-vinylacetamide (NVA) via the sol-gel reactions of tetraethyl orthosilicate (TEOS) on polymer particle surfaces. Different amounts of NVA were used to prepare polystyrene particles using the SFEP process. The particles covered with poly-NVA then underwent the Stöber process to form an outer silica shell. NVA was found to stabilize the polymer colloids and improve their stability by steric effects, even after the positive charge on the polymer surface was partially neutralized by the electrostatically adsorbed TEOS, which tends to induce particle aggregation. Further, the –NH functional groups on NVA catalyzed the hydrolysis of TEOS in the sol-gel reaction to form silica. Consequently, small, monodisperse, and stable core-shell particles were formed despite having a low zeta potential.     

Surface modification of a flexible polyimide film using a reactive fluorinated polymer nanosheet

This paper describes an effective approach to surface modification of a flexible polyimide film using a reactive fluorinated polymer nanosheet. N-(1H,1H-pentadecafluorooctyl)methacrylamide copolymers containing carboxyl group as a reactive moiety form stable monolayer on the water surface and highly ordered reactive polymer nanosheets can be fabricated by the Langmuir-Blodgett technique. This reactive fluorinated polymer nanosheet was utilized to modify the surface properties of polyimide film through its immobilization using thermal treatment. The modification process was studied by X-ray photoelectron spectroscopy (XPS) and modified PI surface was characterized by contact angle measurements and atomic force microscopy (AFM).     

Patterned immobilisation of silicon dioxide nanoparticles on the surface of a photosensitive polymer

A photosensitive co-polymer of styrene and 4-vinylbenzyl thiocyanate was synthesised and employed for the immobilisation of aminofunctionalised silica nanoparticles (SiO₂-NP) at the polymer surface. Upon UV irradiation of the co-polymer, isothiocyanate groups are generated by a photo-isomerisation reaction of the thiocyanate groups. The silica nanoparticles were selectively immobilised in irradiated areas by immersing the illuminated polymer surface in a solution of SiO₂-NP. Depending on the time of immersion and the nanoparticle concentration, different amounts of silica can be deposited in the irradiated areas, whilst no immobilisation of SiO₂-NP is observed in the non-irradiated areas. By using photolithographic methods, patterned silica structures (μm scale) were produced on the polymer surface. The SiO₂-NP covered surfaces are of potential interest to generate protective surface layers and to carry out further functionalisation reactions of the immobilised SiO₂-NP particles.     

Fabrication of porous ceramics with controlled pore size by colloidal processing

Well-defined macroporous ceramics consisting of TiO₂ and ZrO₂ have been fabricated by two methods. One is via a template-assisted colloidal processing technique and the other is via a hetero-coagulation of template/ceramic particle colloidal processing. The former technique is as follows. Close-packed polymer spheres were first prepared as a template using centrifugation or gravitational sedimentation, followed by infiltration with alkoxide precursors. Then the removal of the template beads was achieved by calcination of the organic–inorganic hybrids at appropriate temperatures, yielding well-ordered macroporous ceramics. The latter technique is as follows. Core–shell composites of polymer/ceramic were obtained by mixing the oppositely charged two suspensions via electrostatic attraction following by filtration and calcination to produce macroporous ceramic materials. SEM images revealed that macroporous TiO₂ and ZrO₂ with ordered and uniform macropores have been obtained by both procedures.     

Moduli of ordered polymer composites prepared by colloidal crystallization of nano- and micro-SiO2 spheres in crosslinked methacrylate resins

The extraordinary mechanical performance of nanomaterials found in nature has been attributed to the ordered arrangement of the components. Here, nano- and mico-composites containing either ordered or disordered arrangement of the spheres were compared. The nano- and micro-composites were formed using 19–45 vol% silica in crosslinked resins of triethylene glycol dimethacrylate (TEGDMA) and methyl methacrylate (MMA), in weight ratios TEGDMA/MMA of 100/0, 80/20 or 60/40. The silica nanoparticles, with sizes of 250, 500 and 1000 nm diameter, were silanated with methacryloxypropyl trimethoxysilane (MPS), MPS-SiO₂, to promote bonding to the resin. The ordered nano- or micro-composites were obtained by colloidal crystallization and formed face-centered cubic arrays. Disorder was achieved by mixing two particle sizes or by addition of a coinitiator, dimethylaminoethyl methacrylate (DMAEMA). Ordered nano- or micro-composites had moduli 30% higher than similar composites in which disordered was introduced by mixing two size spheres, at the same loading, for all resin compositions. The greatest improvement occurred at the highest packing density of the spheres, 45 vol%. When disorder was introduced by addition of DMAEMA, the mechanical properties of the ordered and disordered composites were similar, since local but not long-range regions of order was also achieved in the latter case.     

Directed growth of colloidal crystals on a hydrophobic polymer film by using hydrophilic traps

Deposition of colloidal crystal films onto a hydrophobic surface using capillary force-induced self-assembly is difficult to achieve because of wetting problems of the aqueous colloids with the substrate. We present here a method to overcome this problem. By introducing a hydrophilic trench around the hydrophobic polymer, uniform crystalline colloidal films can be deposited onto the surface of the polymer, provided a sufficient volume of suspension is used. The hydrophilic area around the polymer acts like an artificial trap that can help pin the colloidal suspension on the surface of the hydrophobic polymer surface and direct the self-assembly of colloidal spheres, which is the key to fabricate a uniform colloidal crystal film on the polymer surface.     

Characterization of colloidal chromia particles obtained by forced hydrolysis

Colloidal particles of chromia have been prepared by forced hydrolysis of an aqueous solution containing chromium chloride hexahydrate. At elevated temperature, a controlled addition of potassium hydroxide yielded colloidal chromia particles. After the sol coagulation, amorphous dried residues (I) were converted to crystalline form (II) by heating at 1073 K. The thermal treatment was also accompanied by a reduction in both surface area (from 75 to 9 m²/g) and point of zero charge (pH_pzc; from 4.7 to 4.0). Chromia dissolution over the studied pH range (pH=2-12) exhibits a parabolic trend, with minimum solubility at pH_pzc.     

Liquid crystal order in colloidal suspensions of spheroidal particles by direct current electric field assembly

DC electric fields are used to produce colloidal assemblies with orientational and layered positional order from a dilute suspension of spheroidal particles. These 3D assemblies, which can be visualized in situ by confocal microscopy, are achieved in short time spans (t < 1 h) by the application of a constant voltage across the capacitor-like device. This method yields denser and more ordered assemblies than had been previously reported with other assembly methods. Structures with a high degree of orientational order as well as layered positional order normal to the electrode surface are observed. These colloidal structures are explained as a consequence of electrophoretic deposition and field-assisted assembly. The interplay between the deposition rate and the rotational Brownian motion is found to be critical for the optimal ordering, which occurs when these rates, as quantified by the Peclet number, are of order one. The results suggest that the mechanism leading to ordering is equilibrium self-assembly but with kinetics dramatically accelerated by the application of the DC electric field. Finally, the crystalline symmetry of the densest structure formed is determined and compared with previously studied spheroidal assemblies.     

Characteristics evaluation of calcium carbonate particles modified by surface functionalization

Calcium carbonate (CaCO₃) particles were modified by a direct blending method using different coupling agents. The changes in the CaCO₃ particles were determined using different techniques. Compared with pristine particles, the modified CaCO₃ particles show good dispersion, particularly those modified by γ-methacryloxypropyl trimethoxy silane. Results of the thermogravimetric analysis indicated that the coupling agents were adsorbed or anchored on the surface of the CaCO₃ particles, thereby hindering aggregation. The formation of covalent bonds [CaOSi] or [CaOTi] was verified using Fourier transform infrared spectroscopy and X-ray diffraction. The modified CaCO₃ particles showed more stable colloidal dispersion in ethyl acetate than that of pristine CaCO₃ particles. Some silane or titanate coupling agents can be combined with CaCO₃ by covalent bonds, thereby changing the surface properties of CaCO₃ and enhancing dispersion in many organic media. The hydroxyl groups on the surface of CaCO₃ particles can interact with silanol groups or titanate coupling agents forming an organic coating layer.     

Erosion of polymers and polymer composites surfaces by particles

Surface erosion due to solid particle impact is a major concern in engineering applications of handling solid-particulate flow. A semi-empirical model is developed for numerical erosion simulation of polymers and polymer composites. The novelty of the developed model is the correct capturing of the angle of maximum erosion for different erosion modes of polymeric materials and relating it to measurable mechanical properties of the target materials. The model incorporates both the material removal due to elastic–plastic collision of the particles at oblique and normal impact angles. The oblique impact model is derived for ploughing and fracture governed mechanisms of material removal. A simplified correlation is used to consider the relative effect of each mechanism on the total erosion at oblique impact angles. The model indicates the variation in velocity exponent to the mechanism of material removal. The theoretically derived model for single-particle impact is correlated to the available experimental results of multi-particle impacts through the empirical coefficients. The predictions are in good agreement with the extensive literature data for polymers and polymer composites. Further, to propose a single model of erosion for polymer and its composite, the relationship between the empirical coefficients in the developed model and the target material properties is established.     

Geometrical characterization of inkjet-printed conductive lines of nanosilver suspensions on a polymer substrate

The effect of droplet/substrate interactions on the geometrical characteristics such as shape and morphology of as-printed conductive lines of nanosilver suspensions was investigated by varying the surface energy, substrate temperature and droplet spacing. With a plasma surface treatment using a mixture of C₄F₈ and O₂ gases, various surface wettability conditions were obtained that could produce desired droplet diameters on the substrate from 30 μm to 70 μm. The substrate temperature varied from room temperature to 75 °C, and ink droplets ejected from a 30 μm nozzle were printed with various overlaps from 10% to 60%. When printed at room temperature, continuous lines are not formed due to line instability issues such as merging of neighboring droplets and line bulges. By heating the substrates, continuous lines without bulges could be obtained on the relatively hydrophobic substrate because the heat flux from the substrate enhances the evaporation rate of the solvent. The coffee ring effect in the droplets and lines is more enhanced as the substrate temperature increases. This effect is weaker in the lines than in the single droplets due to less edge length in the lines. Under appropriate conditions, well-defined continuous lines could be printed without coffee rings.     

Effect of ion bombardment on the optical properties of LDPE/EPDM polymer blends

Ion bombardment is a suitable tool to improve the physical properties of polymers. In the present study, the effect of ion bombardment on the optical properties of low density polyethylene (LDPE)/Ethylene propylene diene monomer (EPDM) blend (LDPE/EPDM) was studied. Polymer samples was bombarded with 130 keV He and 320 keV Ar ions at fluencies levels ranging from 1 × 10¹³ to 2 × 10¹⁶ ions/cm². The untreated and ion beam bombarded samples were investigated using ultraviolet-visible (UV-Vis) spectrophotometry. The optical band gap (E_g), was decreased from ∼2.9 eV for the pristine sample down to 1.7 eV for the samples bombarded with He and Ar ions at the highest fluences. Change in the optical gap indicates the presence of a gradual phase transition for the polymer blends. Activation energy has been investigated as a function of the ion fluences. With increasing ion fluence, a decrease in both the energy gap and the activation energy was observed. The number of carbon atoms (N) in a formed cluster is determined according to the modified Tauc's equation.     

High-speed fabrication of 3-dimensional colloidal photonic crystal films by slide coating of polymer microspheres with continuous feeding of colloidal suspension

A simple, yet rapid fabrication method for large area colloidal crystal film is demonstrated. Aqueous colloidal dispersion sandwiched between a hydrophobic top cell and a hydrophilic bottom substrate formed a flat meniscus at the drying front, from which high quality colloidal crystal films were obtained within 20 min due to the strong capillary force exerted by accelerated water evaporation aided by hot air blowing. Continuous supply of the suspension enabled the fabrication of the colloidal crystal over large area (> 4 cm²) without significant loss of colloids.     

A constitutive approach for studying concentrated suspensions of rigid fibers in a non ‐ Newtonian Ellis fluid

Abstract

A constitutive model for a semi‐concentrated suspension of rigid fibers in a non‐Newtonian fluid is derived in the present study. This work is extended from a previous work by Dinh and Armstrong which counted rigid fibers suspended in a Newtonian fluid. To investigate the effect of the shear‐dependent suspending fluid on the shear viscosity of suspension, the Ellis fluid is assumed to model such a non‐linear matrix. It is shown that the present derivation, via a cell model, gives an analytic form to calculate the drag coefficient of fibers and to illustrate the influence of material parameters of matrix fluid. The resulting equation gives the bulk stress in terms of an integral over a fourth‐order orientation vector, e, similar to the expression of Doi and Edwards for dense macromolecular fluid. For the purpose of evaluation, the present model attempts to predict the rheological behavior in the inception of flow, steady simple shear flow and stress‐growth experiments.     

Plasmon mediated Brillouin scattering of surface acoustic waves (in different directions to polymer line structures on a silver coated glass substrate)

In this paper measurement on the propagation of Rayleigh waves on the surface of polymer line structures on top of a silver layer were examined by using plasmon mediated Brillouin scattering. The line structures grating constants were 8, 4 and 1 μm. Spectra were recorded with different scattering angles and propagation directions with respect to the line direction. Three Rayleigh modes have been observed in samples with grating constants 8 and 4 μm. In the parallel direction, one mode is unshifted relative to a pure silver surface. In the perpendicular direction there is one unshifted and one shifted mode. The observed shift of 6 μm^− 1 is independent of the grating constant. The 1 μm sample shows a somewhat contrasting behavior. Two different scattering mechanisms, involving surface plasmons at each interface, are proposed to explain the observed effects.     

Film formation mechanism in glass lubrication by polymer latex dispersions

The stabilization of organic coatings by tin dioxide resulting in glass bottle lubrication was investigated on flat glass. The anchoring function of SnO₂ was assessed for a mixture of polyethylene and polymethylmethacrylate. Friction tests in air confirm the SnO₂ anchoring property with the maintaining of the lubricant effect due to the polymer over large sliding distances. The persistence of the polymethylmethacrylate stretching band ν_C = O on significant sliding distances in infrared microscopy experiments shows that the polymer coating stabilization results from the strong adhesion of the polymer on SnO₂. The impact of roughness and surface chemistry on the stabilization of the polymer coating was tested. The suppression of the lubricant effect by surface chemistry alteration or by roughness modification of SnO₂ suggests that roughness and surface chemistry of SnO₂ are both necessary for lubrication.