Characterization of colloidal polymer particles through stability ratio measurements

We propose a general methodology for the estimation of the doublet formation rate constant (proportional to the stability ratio of primary particles) in colloidal dispersions from measurements obtained by common optical techniques, such as dynamic light scattering, static light scattering (nephelometry) or turbidimetry. In contrast to previous approaches relying on the initial slopes of the measured quantities, such as the mean hydrodynamic radius, scattered light intensity or turbidity, we introduce a transformation of the measurables to properly scaled quantities, which grow linearly in time with a slope proportional to the doublet formation rate. Analysis of systematic and random errors allows one to control the error in the estimated value of the aggregation rate. Using this approach, we measured the aggregation rate constant of colloidal polymer particles prepared by surfactant-free emulsion copolymerization of styrene and 2-hydroxyethyl methacrylate (HEMA). It was found that the stability ratio at constant ionic strength decreases with increasing dilution of the original polymer latex. This can be explained by the presence of non-reacted stabilizing species (most likely oxidized HEMA) that desorb from the particle surface upon latex dilution and thus diminish the repulsive interactions between particles. In order to check if the stability of latex particles is influenced by reversibly adsorbed species it is always necessary to perform aggregation experiments at various dilutions.     

Effect of cake layer structure on colloidal fouling in reverse osmosis membranes

A series of reverse osmosis (RO) membrane filtration experiments was performed systematically in order to investigate the effects of various hydrodynamic and physicochemical operational parameters on a cake layer formation in colloidal and particulate suspensions. Bench-scale fouling experiments with a thin-film composite RO membrane were performed at various combinations of trans-membrane pressure (TMP), cross-flow velocity (CFV), particle size, pH, and ionic strength. In this study, silica particles with two different mean diameters of 0.1 and 3.0 μm were used as model colloids. Membrane filtration experiments with colloidal suspensions under various hydrodynamic operating conditions resulted that more significant permeate flux decline was observed as TMP increased and CFV decreased, which was attributed to the higher accumulative mass of particles on the membrane surface. Results of fouling experiments under various physicochemical operating conditions demonstrated that the rate of flux decline decreased significantly with an increase of the ionic strength as well as particle size, while the flux decline rate did not vary when solution pH changed. The experimentally measured cake layer thickness increased with a decrease in particle size and solution ionic strength. Furthermore, the model estimation of cake layer thickness by using a cake filtration theory based on the hydraulic resistance of membrane and cake layer was performed under various ionic strength conditions. The primary model parameters including accumulated mass and specific cake resistance were calculated from the cake layer resistance. This result indicated that the formation of cake layer could be closely related with solution water chemistry. The model estimated cake layer thickness values were in good agreement with the experimentally measured values.     

Competition between micellization and adsorption of diblock copolymers in a colloidal system

Significant adsorption of polystyrene-poly(ethylene oxide) (PS-PEO) diblock copolymers onto PS latex particles in an aqueous dispersion is accomplished through suppression of micelle formation by adding tetrahydrofuran (THF) as a cosolvent. We add THF, a good solvent for the micelle core, to weaken the micelle and allow free chains for adsorption to the colloidal particles. Choosing a PS colloidal particle as the adsorption substrate (thus the adsorbed PS block can fully wet the subsurface), we eliminate the complications which arise from micelle formation on the colloidal surface. Since the PS particles swell in the mixed solvent, the adsorbed PS block may penetrate into the swollen latex core, which is favored for entropic reasons. A subsequent water quench of the system to a low THF solution shrinks the PS particle to its original size while retaining most of the adsorbed polymers. The adsorbed chains cannot be removed by adding surfactants or raising temperature to 90°C, indicating that the adsorbed layer is tightly attached to the surface due to kinetic hinderance of the chains in a confined environment. Neutron scattering experiments is being carried out to settle whether the PS penetrates the PS particle. © 1995 John Wiley & Sons, Inc.     

The preparation and characterisation of polymer latices formed in the absence of surface active agents

Methods have been devised for the formation of monodisperse polystyrene latices in the absence of added surface active agents. The particles are stabilised, as a colloidal dispersion, by surface groupings which are an integral part of the particle and are not removed by dialysis. By suitable variation of the ionic strength of the aqueous phase, the initiator concentration and the polymerisation temperature, the final particle size obtained in single-stage reactions was varied between c. 0.15 and 1.0 μm. The coefficient of variation on particle diameters was usually less than 5%. The ionic strength of the aqueous phase was found to play an important part in determining particle size; this was explained in terms of a limited coagulation process occurring at the stage involving the nucleation of polymer particles. Conductometric titration experiments revealed the presence of sulphate, carboxyl and hydroxyl groups on the particle surfaces. Molecular weight determination of the polystyrene formed showed that this was lower than that formed in conventional emulsion polymerisation.     

Polymer particle adsorption at textile/liquid interfaces: a simple approach for a new functionalization route

The adsorption of amino‐functionalized poly(methyl methacrylate) particles prepared by emulsion polymerization onto polyamide/elastane fibres was investigated. The influence of several physicochemical parameters (pH, ionic strength) on the colloidal stability and surface properties of the cationic latex particles was first examined. Then, particle adsorption was studied as a function of particle concentration, particle size, time, pH and salinity. The results obtained demonstrated that the adsorption process was mainly governed by electrostatic interactions and the adsorption isotherms were analysed on the basis of a Langmuir model. Finally, the effect of washing steps on the adsorbed particles was investigated. The results obtained indicated strong interactions between particles and textile fibres. Copyright © 2012 Society of Chemical Industry     

Role of Interfacial Interactions in the Deposition of Colloidal Clay Particles in Porous Media

Colloidal clay particle transport under saturated conditions is believed to be controlled by its interactions with the surrounding environment. The dominating forces among these interactions are electrostatic forces that are determined by colloidal clay particle and porous medium surface charge density and Lifshitz–van der Waals forces that are determined by colloidal clay particle and porous medium surface thermodynamic properties. Electrostatic forces are greatly affected by solution chemistry in terms of solution ionic strength and pH. In this research, electrostatic and Lifshitz–van der Waals forces of natural colloidal clay particles with a model porous medium of silica sand were quantified at different ionic strength and pH conditions. At the same time, colloidal clay particle transport in the model medium of silica sand was conducted in a laboratory column. The maximum electrostatic forces, F ^EL (max), which occurred when the separation distance between colloidal clay particles and the porous medium was in the range of the sum of the double layer thicknesses of the colloidal clay particles and the porous medium, was found to be the determinant factor for colloidal clay particle deposition in the porous medium. Colloidal clay particle desorption in the porous media was related to the net effect of attractive Lifshitz–van der Waals forces and repulsive electrostatic forces, evaluated at the equilibrium distance where physical contact between the colloidal clay particle and silica sand actually occurred (i.e., affix force). Higher colloidal clay particle desorption was found to coincide with smaller affix force values.     

Preparation of nano‐sized silica/poly(methyl methacrylate) composite latexes by heterocoagulation: comparison of three synthetic routes

Continuing earlier work, 2,2′‐azobis(isobutyramidine) dihydrochloride (AIBA) was used as a cationic initiator to generate positively charged polymers, and promote interaction of these polymers with the negatively charged surface of colloidal silica particles in aqueous solution. Three different synthetic routes have been investigated. In a first route, emulsion polymerization of MMA, initiated by AIBA, was performed directly in an aqueous suspension of the silica beads using a non‐ionic polyoxyethylenic surfactant (NP₃₀). In a second route, AIBA was first adsorbed on the silica surface, and the free amount of initiator was discarded from the suspension. The silica‐adsorbed AIBA adduct was suspended in water with the help of surfactant, and used to initiate the emulsion polymerization of MMA. In a third route, cationic PMMA particles were synthesized separately and subsequently adsorbed on the silica surface. Whatever the approach used for their elaboration, the colloidal nanocomposites were shown to exhibit a raspberry‐like morphology. Quantitative determination of the amount of surface polymer enabled us to evaluate the efficiency of the heterocoagulation process and establish a comparison among the three synthetic routes. Copyright © 2004 Society of Chemical Industry     

Stability of pigment and resin dispersions in waterborne paint

The stability of a colloidal dispersion in a waterborne paint system, which consists of dispersed pigment and polymeric particles (dispersion or emulsion) along with a water-soluble acrylic polymer, was investigated. It was found that adsorption of appropriate ultrafine particles to the relevant particles could stabilize these particles against flocculation, leading to lower viscosity and yield value. The gloss and smoothness of the resultant films are notably improved. As the stability of the colloidal particles in an aqueous system is strongly dependent on the electrostatic effect, the effect was evaluated by measuring the ζ-potentials of the relevant colloidal particles. The ζ-potential is the electric potential on the outside of the surface layer, which includes the counterions around the particle. The ζ-potentials of a series of pigments in a solution of a water-soluble polymer were determined. By arranging the pigments according to their ζ-potentials, an order of basicity-acidity was established for pigments in a waterborne system, and the order was found to be different from that of solventborne systems, thought to be due to adsorbed counterions. After dispersing the pigment sufficiently with an appropriate polymer dispersant, ultrafine particles (of size under 0.05 μm) of lower refractive indexes were adsorbed to the surface of the pigments and polymeric particles. The adsorption layer of ultrafine particles can modulate the ζ-potentials of various colloidal particles to bring them into a certain range, so that the co-flocculation tendency between different colloids is remarkably diminished providing quite stable paint compositions by both electrostatic and steric hindrance effects.     

Electrical Aspects of Adsorbing Colloid Flotation. VI. Electrical Repulsion between Floc Particles

Abstract

Adsorption isotherms are calculated for precipitate and floc foam flotation within the framework of a Gouy-Chapman model which includes both the electrical attractions of the floc particles to the surface and their electrical repulsions for each other. The canonical ensemble is used, and algebraic expressions are found for approximating the sum of products of cluster integrals. Algebraic expressions for the surface excess of adsorbed floc are obtained which involve three reasonably simple integrals. The dependence of the adsorption isotherms on temperature, ionic strength, surface potentials of the floc and the air-water interface, ionic charge, and floc particle size is investigated.     

回灌过程中离子强度和水流流速对胶体粒子在多孔介质中堵塞的影响

人工回灌过程中的堵塞问题一直是影响其推广的瓶颈,目前回灌过程中大颗粒悬浮物导致的堵塞机理研究较多,对胶体类颗粒物的堵塞机理研究相对少。采用室内砂柱实验,研究不同离子强度和不同水流流速条件下胶体在饱和多孔介质中的迁移-滞留特征。选择大肠杆菌为实验胶体,设计在不同离子强度、不同水流条件下的砂柱回灌实验;运用Hydrus-1D软件模拟,拟合穿透曲线后得到表征胶体沉积的相关参数。实验结果表明,在相同的离子强度下,流速增大会促进胶体的迁移,穿透曲线峰值增高,胶体的吸附率减小。在中等离子强度条件下（IS=30、50 mmol·L^-1）流速对胶体的这种影响比在更低的离子强度（≤10 mmol·L^-1）或更高的离子强度（≥300 mmol·L^-1）条件下更为显著;相反地,同一流速条件下,离子强度从10 mmol·L^-1升高到300 mmol·L^-1时,胶体的吸附随着离子强度的增加而迅速增加。从胶体和介质相互作用势能来看,随着离子强度的增加,胶体和砂表面的相互作用增强,有利于胶体吸附在介质表面,增加介质堵塞的概率。但是,在一定的离子强度下,流速的增加产生的水动力剪切力有利于促进胶体的迁移,不利于胶体的吸附或阻塞,减少了微小颗粒堵塞的概率。模拟结果显示吸附速率系数k、最大固相沉积量S_max随着离子强度的增大而增大,随着流速的增大而减小。从整体上来看,回灌过程中胶体微粒的迁移滞留行为主要受控于离子强度,但水流因素会干扰离子强度的控制作用。在实际的人工回灌过程中,有效的预防堵塞需要将化学（降低离子强度）和水动力（增加回灌水流速）手段有效地结合起来。     

Covalent and Ionic States of Strong Acids at the Ice Surface

The relationship between the degree of ionization and the environment of a strong acid is of basic scientific interest. Often this relationship reduces to the interdependence of ion/acid hydration and proton transfer. Despite the presence of pure water, the surface of crystalline ice, particularly at cryogenic temperatures, is one of limited (controlled?) availability of water of hydration. Here, the detailed nature of the ice surface and the states of strong acids adsorbed to ice at cryogenic temperatures are examined. These subjects are of special current interest since the ability to model the complex chemistry that occurs on the surfaces of water-rich particles in the atmosphere, particularly in the stratosphere over the polar regions, requires a valid concept of the acid-ice interface. Our combined spectroscopic and simulation studies have identified the surface of free-standing ice particles as badly disordered, with a range of water-ring sizes and an increased level of H-bond saturation relative to an ordered ice surface. FT-IR results are reported for the interaction of the surface of such ice particles with submonolayer amounts of adsorbed DCl, DBr, and HNO₃ and for multilayer exposure to DCl. The DCl and DBr adsorbed states demonstrate behavior familiar from observations on strongly bound molecular adsorbates. Two methods have been devised for exposure of the nanocrystals to HNO₃ One gives an ionic state initially, while the initial state of the other approach is molecular. In both instances, the system is observed to evolve, with time/warming, towards a common mixed molecular–ionic adsorbed state.     

Thermal oxidation of lipids in monolayers. I. The nature of binding on silica

The purpose of this study was to investigate whether the oxidation of lipids in the ordered state differs from that in the bulk phase. Simple model systems of lipids adsorbed on silica were used as a monolayer model system. This part of the study was designed to provide a better understanding of the nature of lipid adsorption on silica. Isotherms were determined for a number of substrates differing in chain length and functional groups. The number of molecules adsorbed per unit area of silica was found to decrease with increasing chain length. Binding was also dependent on the type of functional group present. For the same length, the amount adsorbed was in the following order: alcohol >acid> ester, whereas binding strength was as follows: acid >ester> alcohol.     

Electrokinetic behaviour of coal particles suspensions

Measurements of the zeta potential of coal suspensions have been carried out by micro-electrophoresis. The influence of colloidal particles concentration, temperature, pH and ionic strength on two types of Spanish coals have been studied. Experimental results are discussed in terms of the adsorptive properties of coal surface and with regard to the formation of aggregates by coagulation.     

Hydration of low porosity slag-lime pastes

Slag-lime pastes of low porosity (water/solid ratio of 0.20) were hydrated from 6 hours to 180 days at 20°C. The kinetics and mechanisms of the hydration process were studied from the results obtained in this investigation. The depth of the hydrated layer on the slag particles is found to be thin indicating that the hydration reaction is very slow. The molar compositions of the formed hydrates could also be calculated from the free lime, nonevaporable water and uncombined slag contents. A high lime product (molar C/S+A ratio of 2.5–2.6) is formed during the early stage of the hydration process, then the molar C/S+A ratio drops to a value of 1.5 and finally rises to a value of 1.7 at 180 days. The surface areas and pore volumes of hydrates were determined from water and nitrogen adsorption measurements. For water vapor adsorption, the water molecules in the adsorbed phase seem to be highly oriented in an ordered array. This effect might be associated with the polar character of water molecule, when adsorbed on an ionic surface like high lime hydrate. The results of x-ray diffraction and SEM observations indicate only the formation of ill-cyrstallised hydration products.     

Effects of addition of colloidal silica particles on TEOS-based stone protection using n-octylamine as a catalyst

Protective agents based on tetraethoxysilane (TEOS) have been widely used for the protection of stone heritages. However, TEOS-based protective agents suffer from practical drawbacks, such as crack formation of the gel during the drying phase due to the developed capillary force, which is typical for TEOS-based protective agents. In this paper, we have prepared new TEOS-based protective agent containing flexible hydroxyl-terminated polydimethylsiloxane (PDMS-OH) and colloidal silica particles (167 nm) using n-octylamine as a catalyst in order to reduce capillary force development and increase hydrophobicity, and have characterized them for the application of stone protective agent. The extent of surface hydrophobization depends on concentration of colloidal silica particles and reaches a maximum value of 123° at 0.2% (w/v) of colloidal silica particles for the case of treated with the modified composition. The presence of n-octylamine is a key factor which promotes the increase of the gel pore size. The protective performances were also evaluated by its ability to resist acid corrosion. The results reveal that the protective effects are satisfying.     

Hydrothermally treated chitosan spontaneously forms water-soluble spherical particles stable at a wide pH range

The authors report the spontaneous formation of water-soluble chitosan-tartaric acid (CS-TA) spherical particles. Particles are formed by heating chitosan in the presence of tartaric acid under hydrothermal conditions. Tartaric acid serves as an ionic cross-linker, a depolymerizing agent, and a particle stabilizer in aqueous phase. The CS-TA particles exhibit superior colloidal stability at a wide pH range due to their surface charge tunability, which is due to the colocalization of surface hydroxyl, amine, and carboxyl groups. At physiological pH condition, particles have zwitterionic structure as determined by the zeta potential measurements. Still, CS-TA maintains colloidal stability at neutral pH due to the abundance of surface hydroxyl groups. As a proof-of-concept study, the CS-TA particles were labeled with a model insoluble cargo (fluorescein isothiocyanate [FITC]) to demonstrate their capacity for solubilizing hydrophobic drugs. The CS-TA/FITC conjugates were found to remain well dispersed at neutral pH, while maintaining FITC fluorescence properties.     

An EPR study of Cu adsorption by clinoptilolite from Cl<Superscript>−</Superscript>, NO<Stack><Subscript>3</Subscript><Superscript>−</Superscript></Stack> and SO<Stack><Subscript>4</Subscript><Superscript>2−</Superscript></Stack> solutions

The concentration and the type of Cu²⁺ species adsorbed on a natural zeolite (Clinoptilolite) was measured and studied by using Electron Paramagnetic Resonance Spectroscopy (EPR). The EPR results together with macroscopic sorption data indicate that the solution ionic strength as well as, the type of electrolyte anion (Cl⁻, NO₃⁻ and SO₄²⁻ ions were examined) affect the amount of Cu adsorbed and the type of Cu surface complexes. The increasing in solution pH affects Cu adsorption quantitatively whereas; the type of surface complexes formed depends mainly on solution ionic strength. For low solution ionic strength, when the inhibition from solution species is limited, the adsorbed Cu is characterized by more than one type of chemical environment. On the contrary, for high solution ionic strength the Cu adsorption is inhomogeneous and EPR spectra show only one type of surface complex. When the anions of the background electrolytes are different, but of equal normality, the results indicate that in the presence of SO₄²⁻ discernible Cu surface complexes are formed whereas, for Cl⁻ and NO₃⁻ these surface formations are obtained only for high Cu adsorbed concentrations.     

Thin films of amphiphilic polyelectrolytes. Soft materials characterized by Kelvin probe force microscopy

Hydrophobically modified amphiphilic polyelectrolyte films derived from poly (maleic anhydride-alt-styrene) containing hydrophobic aryl-alkyl type side chains such as phenyl-ethyl, phenyl-butyl, naphthyl-ethyl and naphthyl-butyl were studied by Kelvin probe force microscopy. These films were adsorbed from polyelectrolyte solutions at 0.001 mol/L and 0.1 mol/L NaCl onto silicon wafers modified with 3-aminopropyltrimethoxysilane. At high ionic strength, the work function was dependent on the hydrophobic character of the side chain. At low ionic strength this behavior was determined by the spacer group in the side chain. The fractal analysis of the films indicated self-affinity surfaces whereas the fractal dimensions of the surface topography follow a similar trend as the electronic work function with the ionic strength. This behavior can be explained by the increasing hydrophobic character of the side chain with naphthyl moieties. Relationship between the molecular structure and the fractal dimensions with the work function of the adsorbed polyelectrolytes was found.     

Colloidal Stability and Titania Precipitate Morphology: Influence of Short-Range Repulsions

For a wide range of reagent concentrations, particles formed from the hydrolysis of tetraethyl orthotitanate in aqueous ethanol solutions fall into two morphological types. In the first, the particles are composed of uniform spheres, while in the second, the precipitate consists of agglomerates of discrete particles which have been fused together by further reaction products. To explain this observation, we develop a growth mechanism where colloidal stability is imparted to the growing particles through a combination of electrostatic and short-range repulsions giving rise to a shallow secondary minimum which develops for certain particle sizes and results in the formation of doublets that can be fused together. If the particle surface potential is of sufficient magnitude, the secondary minimum is no longer accessible by Brownian motion and uniform precipitates result. The effects of particle surface potential and reaction medium ionic strength are discussed.     

Fabrication of chemically bonded polyacrylate/silica hybrid films with high silicon contents by the sol–gel method

Polyacrylate/silica hybrid latexes (PAES) with high silicon contents (up to 21%) were prepared by directly mixing colloidal silica with polyacrylate emulsion (PAE) modified by a silane coupling agent. Sol–gel-derived organic/inorganic thin films were obtained by addition of hydrophilic co-solvents to PAES and subsequent drying at room temperature. The effects of co-solvents and γ-methacryloxypropyltrimethoxysilane (KH570) content on the properties of PAES films were investigated. Dynamic light scattering (DLS) data indicated that the average diameter of PAES (96 nm) was slightly larger than that of PAE (89 nm). TEM photo revealed that colloidal silica particles were dispersed uniformly around polyacrylate particles and that some of the colloidal silica particles were adsorbed on the surface of PAE particles. The data of crosslinking degree and FT-IR spectra confirmed that the chemical structure of the PAES changed to form Si–O–Si-polymer crosslinking networks during the film formation. AFM photos, contact angle for water, and XPS analysis showed that the polyacrylate/inorganic hybrid films with high silicon contents were formed by the co-solvent-mediated, sol–gel method and that the Si-based polymers were uniformly distributed on the surface of the dried films. TGA data demonstrated that the PAES films display much better thermal stability than the PAE counterpart.