Characterization of Sub‐Micron Perovskite Suspensions Formed Through Cavitation Processing

The size distribution within and electrokinetic properties of aqueous perovskite (LaCoO₃) suspensions, have been characterized as a function of processing conditions. Submicron–sized perovskite particles have been obtained using a cavitation technique in which the suspension is passed through a series of small orifices under extreme driving pressure drops. When no additives were used, the zeta potential of the particles was found to be positive over the entire pH range studied. Use of an acrylic copolymer surfactant with multiple negatively charged sites during the cavitation processing was found to improve dispersion stability. The observed variations in zeta potential and particle size for the suspensions are explained in terms of electrostatic interactions between particles, the tendency for the surfactant to adsorb onto the particles, and the degree of steric stabilization provided by the surfactant.     

Electrostatically mediated adsorption by nanodiamond and nanocarbon particles

Nanodiamond (ND) and other nanocarbon particles are popular platforms for the immobilization of molecular species. In the present research, factors affecting adsorption and desorption of propidium iodide (PI) dye, chosen as a charged molecule model, on ND and sp ² carbon nanoparticles were studied, with a size ranging from 75 to 4,305 nm. It was found that adsorption of PI molecules, as characterized by ultraviolet–visible spectroscopy, on ND particles is strongly influenced by sorbent-sorbate electrostatic interactions. Different types of NDs with a negative zeta potential were found to adsorb positively charged PI molecules, while no PI adsorption was observed for NDs with a positive zeta potential. The type and density of surface groups of negatively charged NDs greatly influenced the degree and capacity of the PI adsorbed. Ozone-purified NDs had the highest capacity for PI adsorption, due to its greater density of oxygen containing groups, i.e., acid anhydrides and carboxyls, as assessed by TDMS and TOF–SIMS. Single wall nanohorns and carbon onion particles were found to adsorb PI regardless of their zeta potential; this is likely due to π bonding between the aromatic rings of PI and the graphitic surface of the materials and the internal cavity of the horns.     

Application of the density functional method to study phase transitions in an associating Lennard-Jones fluid adsorbed in energetically heterogeneous slit-Like pores

A density functional approach is used to study the adsorption of the four-bonding-site model associating Lennard-Jones fluid in slit-Like pores with energetically heterogeneous walls. The fluid-wall potential is qualitatively similar to that invoked by Röcken, P., Somoza, A., Tarazona, P., and Findenegg, G. H., 1999, J. chem. Phys., 108, 8089, i.e. it consists of a homogeneous part that varies in the direction perpendicular to the wall and a periodic part, varying also in one direction parallel to the wall. Both parts are modelled by Lennard-Jones 9,3-type functions. The structure of the adsorbed film is characterized by the local densities of all particles and the densities of the monomers. The phase diagrams are evaluated for several systems characterized by different corrugation of the adsorbing potential. The adsorbing field is strong enough to allow for the layering transition. As well as the formation of the so-called bridge phase that fills the pore space over the most energetic parts of the wall and of capillary condensation, the layering transition is observed within the first layer adjacent to the pore walls. If the adsorbing potential due to each pore wall is shifted in phase by π/2, the bridge phase is not formed.     

Molecular mobility in fixed-bed reactors investigated by multiscale NMR techniques

The complex problem of a fixed-bed reactor consisting of catalytically active particles provides an exceptional opportunity of combining a wide range of NMR methods which have become available over time as tools to probe porous media. This work demonstrates the feasibility of different NMR techniques for the investigation of the intra- and interparticle pore space over length scales from nanometers up to centimeters. Many industrially relevant cracking reactions leave a coke residue on the inner surface of the porous catalyst particles so that the active sites become inaccessible to the reactants. Moreover, the pore space shrinks due to the formation of coke, thereby hindering molecular transport. The presence of the coke residue and its influence on the mobility of adsorbed fluid molecules are probed by 129Xe spectroscopy, NMR cryoporometry, relaxation dispersion measurements, and investigations of the reduced diffusivity in the intraporous space. The voids surrounding the random arrangement of catalyst pellets represent another pore space of much larger dimensions, the properties of which can be more directly investigated by mapping the fluid density and the velocity distribution from velocity-encoded imaging. Propagator representations averaged over large sample volumes are discussed and compared to velocity images obtained in selected axial slices of the reactor.     

基于岩石重构图像的核磁共振响应模拟

能够反映孔隙介质内部真实复杂结构的CT图像经常被用于模拟研究中并能取得较好的结果. 但是,在很多情况下缺少三维CT图像或者其分辨率受限,此时,更易于获取的二维薄片图像被用于构建三维的孔隙结构图像. 假定孔隙介质各向同性,基于二维图像,使用多点统计方法可以构建岩石的三维孔隙结构. 基于数字图像,采用随机游走方法模拟得到核磁共振响应,然后由模拟得到的回波串反演得到T₂分布. 研究表明,岩石重构图像中的模拟结果与CT图像中的模拟结果有较好的一致性. 基于数字图像的核磁共振响应模拟为分析不同孔隙结构的核磁共振响应提供了便利,同时,模拟结果也为验证孔隙结构的重构效果提供了依据.     

Application of the kinetic Monte Carlo method in the microscopic description of argon adsorption on graphite

We present an application of kinetic Monte Carlo (kMC) in the canonical ensemble to a calculation of vapour liquid equilibrium and to describe the adsorption of argon on a flat graphite surface and in a slit-like graphitic pore. Simulations at 77 and 87.3?K accurately describe the experimental data. The kMC method is simple to implement and, unlike conventional Monte Carlo, no rejection trials are necessary. The only move is a uniform sampling of the volume space, which makes the determination of the chemical potential straightforward using real particles in the simulation, in the same spirit as the Widom inverse potential distribution. This avoids the need to freeze the real particles before the trial insertion of test particles as is necessary in other methods, such as the Widom method and its variants.     

Electrokinetic potential reduction of fine particles induced by gas nucleation

Electrokinetic potential of particles has been extensively studied in colloidal systems over the past century, while up to date, the influence of gas on electrokinetic behaviors of particles has not been fully understood yet. In this study, the electrokinetic response of particles to gas nucleation was systematically investigated with coal as the object. The results showed that the nucleation of gas (both on particle surfaces and in water) significantly changed the particle’ electrokinetic behaviors. Higher gas content and particle’s surface hydrophobicity normally trigger more intensive gas nucleation, thus inducing more significant reduction of particle zeta potential. After gas nucleation, numerous nanobubbles (NBs) appear in the suspensions mainly in two forms: NBs adhering onto solid surfaces (ANBs) and NBs stagnating in bulk solutions (BNBs). ANBs not only enhance the surface heterogeneity, but also cause the “steric hindrance” effect, and electric double layer (EDL) overlapping and associated ions shielding towards charged particles, which significantly decrease their electrokinetic potentials. Although BNBs can also reduce the zeta potential of particles by EDL compressing, their functions are rather limited.     

An Electroacoustic Investigation of Concentrated Aqueous Suspensions of Calcium Pyrophosphate

The zeta potential of concentrated suspensions of calcium pyrophosphate were investigated using electroacoustics. The particles were negatively charged over the entire pH range studied. It proved impossible to reduce the pH of the suspension below 1.8, but the iso electric point could be estimated to occur at approximately pH 1. Two commercially available dispersants (one cationic and one anionic) were then added in small increments to the suspension in order to follow the change in zeta potential as the dispersants adsorbed onto the particles. From the shape of the curve it was possible to estimate the optimum adsorbed amount of dispersant required to fully coat the particles. The cationic dispersant adsorbed strongly and the optimum dosage was estimated at 2.5 ml of active polymer/kg of powder. Anionic dispersants are known to adsorb onto negatively charged ceramic oxide particles, but the anionic dispersant used in this study did not adsorb onto the negatively charged calcium pyrophosphate particles.     

Physical and chemical properties of Co n?m Cu m nanoclusters with n?=?2–6 atoms via ab-initio calculations

The aim of this work is to investigate the influence of the preparation method on the surface charge and electrokinetic properties of poly-??-caprolactone-based particles using poloxamer 188 as stabilizing agent. To target such objective, two processes (the nanoprecipitation and the emulsification-diffusion) are used to prepare well-defined nanospheres ranging in hydrodynamic diameters from 100 to 200?nm. The effect of the materials used on the particle zeta potential is systematically studied to compare the two preparation methods. The polarity of the organic solvent directly affects the zeta potential of particles prepared via the emulsification-diffusion method. The results obtained suggest that the aqueous phase used for preparing particles affects the possible re-arrangement of polymers during the emulsification step. As the aqueous phase is saturated with the organic solvent, the polar and the non-polar moieties of the polymer chains might be re-conformed following organic solvent diffusion from the particle core to the continuous phase. Regarding the nanoprecipitation process, the electrokinetic properties of the particles were found to be organic solvent independent, but principally affected by the pH and the salinity of the aqueous phase used during the particle preparation.     

Fabrication of diarylide yellow pigments/modified SiO2 core-shell hybrid composite particles for electrophoretic displays

Diarylide yellow pigments/modified SiO₂ core-shell hybrid composite particles were fabricated via a newly developed two-step procedure. The surface of diarylide yellow pigments was coated with SiO₂ by the hydrolysis of Na₂SiO₃. The obtained particles were then modified with in situ generated 3-aminopropylsilanetriol or succinic acid to form composite particles containing amino or carboxyl groups. The FT-IR spectra, TGA and TEM showed that the particles had a core-shell structure, the SEM suggested that the surface morphology of the composite particles was smooth, and the XPS and zeta potential measurement indicated that the composite particles had a high charge load. The obtained composite particles have been applied as electrophoretic particles in the electronic paper, which demonstrated that the newly developed procedure is an effective way to produce various organic/inorganic composite particles used for electrophoretic displays.     

Studies of the anisotropy of the microstructure of oil and gas reservoir rocks by electron microscopy methods

The paper presents the features of applying the scanning electron microscopy method for studying the anisotropy of the pore space of carbonate rocks in oil and gas reservoirs. The results of studies into the horizontal anisotropy of the microstructure and pore space are presented. The significance of the pore space horizontal anisotropy for filtration properties, which should be taken into account during the development of 3D-hydrodynamic models of hydrocarbon deposits, has been experimentally found for rocks with a complex structure.     

Particles size effects of single domain CoFe2O4 on suspensions stability

Single domain magnetic CoFe₂O₄ nanoparticles with spinel structure were prepared by the coprecipitation method. Particles with size of 16, 20, 40 and 60 nm were synthesized by sintering the precursor at 500, 600, 800 and 900 °C, respectively. The magnetic hysteresis measurement of CoFe₂O₄ particles showed that particles were single domain particles with similar saturation magnetization (∼300 emu/cm³) at room temperature. The zeta potential study of suspensions (CoFe₂O₄-acetylacetone system) with various particle sizes showed the suspension systems had similar zeta potential values (∼40 mV). The effects of magnetic particle size on the suspension stability characterized by electrophoretic deposition yields and sediment volumes were studied. The suspension stability decreased with an increase in particle size and a flocculation threshold of particle radius a was found at 30 nm. A suspension stability theory approaching to the phenomenon was established. The theory based on the DLVO theory was developed by introducing an extra magnetic interaction force. Dormann model was adopted, in which the magnetic interactions of two spherical nanoparticles were investigated in terms of dipole-dipole interactions. Compared to DLVO, suspension's physical parameters not only zeta potential ζ and the Debye length 1/κ, but also particles' radius a brought about stable to flocculation transition in the theory.     

Structure and phase transitions in a network-forming associating Lennard-Jones fluid in a slit-like pore: a density functional approach

A study is reported of adsorption of an associating Lennard-Jones fluid with four associative sites per molecule in a slit-like pore. The density distribution of particles in the pore and thermodynamics properties are evaluated by using a density functional method. It is found that at low temperatures the fluid exhibits a set of layering transitions, followed by capillary condensation. Transitions are localized by analysing the grand canonical potential. The density profiles of particles and the distribution of unbound and differently bonded particles demonstrate changes in the structure of the fluid in the pore along the phase coexistence. The critical temperature is lower for a confined fluid, compared with the bulk counterpart. However, an increase in the energy of association increases the critical temperature. The envelope of the capillary condensation is narrower than the bulk liquid-vapour phase diagram. The dependence of the solvation force on the energy of association and on the bulk density is discussed.     

Phosphonated Polyethylenimine‐Coated Nanoparticles: Size‐ and Zeta‐Potential‐Adjustable Nanomaterials

Novel partially phosphonated polyethylenimine polymers are developed in order to control the modification of nanoparticle (NP) surfaces. This polymer is built by an accessible one‐step process. The numerous phosphonate functions assume both a strong covalent anchoring on metal oxide NPs and a modulation of electric charges, while amino groups are associated with dispersion preservation and subsequent biofunctionalization. The zwitterionic nanomaterials obtained display a good stability toward pH and ionic strength. According to the selected percentage of phosphonation and the polymer size, zeta potential, and diameter of the particles are controlled.     

Preparation of low density TiO2/poly (methyl methacrylate) composite particles by emulsifier-free emulsion polymerization

Based on the 3-(trimethoxysilyl) propylmethacrylate (MPS) modified TiO₂ particles, the TiO₂/poly (methyl methacrylate) (PMMA) composite particles have been prepared successfully via emulsifier-free emulsion polymerization in water. A facile floating-sinking method is proposed to roughly evaluate the composite particles’ density. Chemical component of obtained composite particles was identified by Fourier transform infrared spectra (FTIR). The morphology and grain size of the composite particles were investigated by field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). Thermal analysis of the composite particles was measured by differential thermal analysis-thermo gravimetric analysis (DTA-TGA). The zeta potential and electrophoretic mobility of composite particles with suitable density in water was measured by dynamic light scattering (DLS).     

Low oil emulsion gel stabilized by defatted Antarctic krill (Euphausia superba) protein using high-intensity ultrasound

Emulsion gels with low oil contents have been continuously developed in recent decades. In this study, the use of high-intensity ultrasound for the preparation of low oil emulsion gel (oil fraction of 0.25) was investigated. Specifically, defatted Antarctic krill protein (dAKP) was used to stabilize the interface of soybean oil and water. Then, the microstructure and the stabilization mechanism of the formed emulsion gel were evaluated by cryo-SEM, CLSM, zeta potential, rheological measurements, and FTIR. Besides, the particle diameter was measured to be around 5 μm. The results of CLSM indicated that the emulsion gel was the oil-in-water type. The emulsion gel exhibited gel-like viscoelastic behavior even at a low concentration of dAKP due to the formation of a rigid particle network while the rheological behavior of the emulsion gel was significantly affected by the concentration of dAKP. The stabilization of the emulsion gel can be maintained by space steric hindrance and hydrophobic interactions between particles in the emulsion gel system.     

Preparation of Fe3O4/poly(styrene-butyl acrylate-[2-(methacryloxy)ethyl]trimethylammonium chloride) by emulsifier-free emulsion polymerization and its interaction with DNA

Cationic magnetic polymer particles Fe₃O₄/poly(styrene-butyl acrylate-[2-(methacryloxy)ethyl]trimethylammonium chloride), a type of potential gene carrier, were prepared by emulsifier-free emulsion polymerization with oleic acid modified magnetite Fe₃O₄, styrene, butyl acrylate and [2-(methacryloxy)ethyl]trimethylammonium chloride) (METAC). The morphology of the particles was characterized by transmission electron microscopy and the composites of particles were characterized by FT-IR spectroscopy, X-ray diffraction. These results showed that magnetic particles were well dispersed in polymers with the content of about 15%(wt/wt). The composites exhibited superparamagnetism and possessed a certain level of magnetic response. The interactions between the particles with calf-thymus DNA (ct DNA) were confirmed by zeta potential measurement, UV-vis spectroscopy and fluorescence spectroscopy. The DNA-binding capacity determined by the agarose gel electrophoresis showed good binding capacity of the emulsion to DNA. These results suggested the potential of the cationic magnetic polymer emulsion as gene target delivery carrier.     

The influence of dust particle geometry on its charge and plasma potential

In this paper, a self‐consistent numerical model describing the behaviour of plasma around isolated highly charged dust particles with different shapes of rotation figures is presented. Dust particles in the form of a sphere, oblate ellipsoids (disk‐like particles), and elongated ellipsoids (rod‐like particles) are considered in the presence of an external electric field. Using the developed model, self‐consistent distributions of a space charge and plasma potential are obtained around non‐spherical dust particles. These distributions are carefully analysed by decomposing them in a series of Legendre polynomials. Decompositions of these distributions are compared with particles of different geometry. In addition, for different geometries of dust particles, the dependencies of the charge of a dust particle on geometry in the absence of an external field are investigated.     

Degree of Flocculation and Interparticles Charges of Conditioned Municipal Activated Sludge using Mixed Polymers

The present research work focuses on a new conditioning and flocculation mechanism of municipal fresh activated sludge using a dual polymer system combining cationic and anionic polyelectrolytes. Various pairs of three different types of polyelectrolytes, low molecular weight cationic polyacrylamide (CPAM-10), high molecular weight cationic polyacrylamide (CPAM-80) and an anionic polyacrylamide (APAM-30), were selected, being used either individually or as cationic-anionic pairs. The results of use of the dual systems indicated that using mixed polymers for conditioning gave lower turbidity with better settling when compared to that of using individual pure polymers. The mixed polymers improved the sludge volume index (SVI) by 62%. The zeta potentials of the supernatant and solid-like samples of conditioned activated sludge were measured. Slight increases in zeta potential, from –12 to –9, of the mixed polymers for all supernatants were observed. On the other hand, zeta measurements showed that the sludge solid-like particles retained their negative charges despite the addition of the individual cationic polymers in the mixture. This phenomenon was explained in terms of the addition of the polyelectrolytes attracting, primarily, the carboxylic groups of the fine suspended sludge particles, while hydrogen bonds between the larger sludge particles resulted in attraction in accordance with the Van der Waals mechanism, and both attractions caused an immediate dewatering that led to flocculation, but with low compactness. As a result of retaining negative charges on the large sludge particles, dissolved metals were partially attracted, causing reduction in conductivities of the supernatants of 10% to 15% for all pairs. Rheological tests showed that the formed flocs had low shear stress resistances, ranging between 0.2 and 0.4 Pa, and weak flocs strength.     

Tracer diffusion in fibre networks: the impact of spatial fluctuations in the fibre distribution

A mean-field formalism that addresses spatial non-uniformities in fibre networks is combined with the cylindrical cell model to calculate the diffusion constant for a spherical tracer. Deviations from randomness in the fibre distribution are described by an operational distribution over volume fractions that is parametrized by mean values for the pore radii and void space chord lengths. Weight factors for elements with different radii in the cell model are assigned in a manner that enforces agreement with the distribution over pore sizes predicted by our treatment of heterogeneous networks. Illustrative calculations suggest that the tracer diffusion constant is quite sensitive to non-uniformities in the network, particularly for tracer particles with radii that are large compared to the fibre diameter.