Single step hybrid coating process to enhance the electrosteric stabilization of inorganic particles

We report on a single-step coating process and the resulting colloidal stability of silica-coated spindle-type hematite nanoparticles (NPs) decorated with a layer of poly(acrylic acid) (PAA) polyelectrolyte chains that are partially incorporated into the silica shell. The stability of PAA coated NPs as a function of pH and salt concentration in water was compared to bare hematite particles and simple silica-coated hematite NPs, studying their electrophoretic mobility and the hydrodynamic radius by dynamic light scattering. Particles coated with this method were found to be more stable upon the addition of salt at pH 7, and their aggregation at the pH of the isoelectric point is reversible. The hybrid coating appears to increase the colloidal stability in aqueous media due to the combination of the decrease of the isoelectric point and the electrosteric stabilization. This coating method is not limited to hematite particles but can easily be adapted to any silica-coatable particle.     

Colloidal stability of magnetite/poly(lactic acid) core/shell nanoparticles

In this work, we describe an experimental investigation on the colloidal stability of suspensions of three kinds of particles, including magnetite, poly(lactic acid) (PLA), and composite core/shell colloids formed by a magnetite core surrounded by a PLA shell. The experiments were performed with dilute suspensions, so that recording the optical absorbance with time gives a suitable indication of the aggregation and sedimentation of the suspensions. The method allowed us to distinguish very accurately between the different surface and magnetic forces responsible for the structures acquired by particle aggregates. Thus, the pure PLA suspensions are very sensitive to ionic strength and almost unaffected by pH changes. On the contrary, the stability of magnetite systems is mainly controlled by pH. The effect of vertical magnetic fields on the stability of magnetite and magnetite/PLA suspensions is also investigated. The PLA shell reduces the magnetic responsiveness of magnetite, but it is demonstrated that the mixed particles can also form structures induced by the field, despite their lower magnetization, and they can be considered in magnetically targeted biomedical applications.     

Stability of dispersions of colloidal alumina particles in aqueous suspensions

The colloidal stability of suspensions of alumina particles has been investigated by measuring particle size distribution, sedimentation, viscosity, and zeta potential. Alumina particles were found to be optimally dispersed at pH around 3 to 7.8 without dispersant and at pH 8.5 and beyond with dispersant. The above results corroborate zeta potential and viscosity measurement data well. The surface charge of alumina powder changed significantly with anionic polyelectrolyte (ammonium polycarboxylate, APC) and the iep shifted toward more acidic range under different dispersant conditions. It was found that the essential role played by pH and dispersant (APC) on the charge generation and shift in the isoelectric point of alumina manifests two features: (i) the stability decreases on approaching the isoelectric point from either side of pH, and (ii) the maximum instability was found at pH 9.1 for alumina only and at pH 6.8 for alumina/APC, which is close to the isoelectric points for both the system, respectively. Using the model based on the electrical double-layer theory of surfactant adsorption through shift in isoelectric points, the authors could estimate the specific free energy of interaction (7.501 kcal/mol) between particles and dispersant. The interaction energy, zeta potential, sedimentation, and viscosity results, were used to explain the colloidal stability of the suspension.     

Electrical surface charge and potential of hematite/yttrium oxide core–shell colloidal particles

Interest in the synthesis of composite colloidal particles consisting of a core and shell with different compositions stems from the fact that such particles can be useful in processes where the properties of both core (e.g., size and shape homogeneity, ease of preparation in large amounts, magnetic characteristics, etc.) and shell (interfacial properties, porosity, chemical stability, etc.) might be of interest. However, the applicability must be based on a proper characterization of those properties. In this work, colloidal spheres of hematite (α-Fe₂O₃) were used as nuclei of mixed particles where the shell is yttrium oxide. The electrical properties of the aqueous interface are compared to those of the pure oxides by means of potentiometric titration of their surface charge and potential against pH, as a function of indifferent electrolyte concentration. It is found that the mixed particles efficiently mimic yttrium oxide, since the behavior of their surface electrical characteristics closely resembles that of the latter compound. Differences are found, however, that can be ascribed to an incomplete or porous coverage, but such divergences are of little significance when an overall comparison is carried out. Received: 30 January 2001 Accepted: 11 July 2001     

Effects of amino acids on the formation of hematite particles in a forced hydrolysis reaction

The influence of amino acids on the formation of hematite particles from a forced hydrolysis reaction of acidic FeCl3 solution was examined. The spherical particles were produced on the systems with L-phenylalanine (L-Phe), L-serine (L-Ser) and L-alanine (L-Ala), though L-glutamine (L-Gln) and L-glutamic acid (L-Glu) gave ellipsoidal hematite particles. This morphological change in hematite particles is consistent with the order of stability constant of amino acids against to Fe3+ ions (K). The hematite particles produced with L-Glu, L-Gln and L-Ser were highly porous because they are formed by aggregation of cluster particles. These particles exhibited microporous behavior by outgassing the particles below 200 degrees C while they changed to mesoporous after treating above 300 degrees C by elimination of amino acids molecules remained between the cluster particles within the hematite particles. The hematite particles strongly depended on the nature of amino acids such as alternation of solution pH and adsorption affinity to beta-FeOOH and/or polynuclear primary (PN) particles. The systems on L-Ala and L-Phe, showing very rapid phase transformation from beta-FeOOH to hematite, exhibited the Ostwald ripening. A rotational particle preparation procedure suggested that the morphology of hematite particle is governed by the mode and strength of amino acid adsorption onto beta-FeOOH and/or PN particles.     

Some aspects of polymer colloids I. Preparation and properties of different types of latex particles

The boundary region separating a latex particle from the surrounding medium has a great influence on the properties of latex dispersions. Four types of polystyrene and polystyrene/comonomer latices differing greatly in the structure of the boundary region were prepared. The first part of a series of papers reports on the preparation of the various latex dispersions. Mean particle sizes were obtained from simple turbidity measurements, quasi-elastic light scattering, and electron micrographs. The behavior of the particles in the centrifugal force field is a simple tool for detecting aggregation tendencies that are not directly related to salt stability. The BET-surface area agrees with the area calculated from the mean particle size when a sharp boundary and smooth surface is developed between the particle and the surrounding medium. In the case of particles with extended boundary regions (core/shell particles or particles with hairy envelopes), film formation reduces the specific surface area. Removal of soluble oligomers and polymers from the boundary region during subsequent treatments (purification and centrifugation before freeze-drying) can increase the surface area considerably.     

Adsorption of barium and calcium chloride onto negatively charged alpha-Fe(2)O(3) particles

Adsorption of cations (Na(+), Ca(2+), Ba(2+)) onto negatively charged (pH 10.4) hematite (alpha-Fe(2)O(3)) particles has been studied. The oxide material was carefully prepared in order to obtain monodisperse suspensions of well-crystallized, quasi-spherical particles (50 nm in diameter). The isoelectric point (IEP) is located at pH 8.5. Adsorption of barium ions onto oxide particles was carried out and the electrophoretic mobility was measured throughout the adsorption experiment. Comparison with calcium adsorption at full coverage reveals a higher uptake of Ba(2+). In both cases it shows also that chloride ions coadsorb with M(2) ions. Simultaneous uptake of the positive and negative ions explains why the electrophoretic mobility does not reverse to cationic migration. A theoretical study of the surface speciation has been carried out, using the MuSiC model. It reveals the presence of negative as well as positive sites on both sides of the point of zero charge (PZC) of the hematite particles, which may explain the coadsorption of Ba(2+) and Cl(-) at pH 10.4. The effective charge of the oxide particles, calculated from the electrophoretic mobility, is in very good agreement with the results found with the MuSiC modelization and the chloride/barium adsorption ratio. It also verifies the theory of ionic condensation. Calorimetric measurements gave a negative heat for the overall reaction occurring when Ba(2+)/Cl(-) ions adsorb onto hematite. Despite the fact that anions (Cl(-) and OH(-)) adsorption onto mineral oxides is an exothermic phenomenon, it is likely that barium and calcium adsorption is endothermic, denoting the formation of an inner-sphere complex as reported in the literature.     

Effects of surfactants and pH of medium on zeta potential and aggregation stability of titanium dioxide suspensions

The effects of benzethonium chloride, sodium dodecylbenzenesulfonate, and 4-(1,1,3,3-(tetramethylbutyl)phenyl poly(ethylene glycol) on the zeta potential and aggregation stability of aqueous rutile-form titanium dioxide suspensions are studied in the pH range of 2–12. It is shown that the nonionic surfactant does not affect significantly the zeta potential and aggregation stability of the suspensions. The influence of ionic surfactants on the aggregation stability of the suspensions considerably depends on the pH of a medium. At pH values above the isoelectric point of titanium dioxide suspensions (pH₀ = 6.2), the suspensions demonstrate a high aggregation stability in the presence of the anionic surfactant, sodium dodecylbenzene-sulfonate (irrespective of its content), while, at pH < pH₀, the aggregation stability of the suspensions markedly increases with the surfactant concentration. In the presence of the cationic surfactant, benzethonium chloride, the aggregation stability of the suspensions is independent of the surfactant concentration at pH < pH₀, whereas, at pH > pH₀, it increases with the surfactant concentration.     

Preparation of low-density 90Y microspheres consisting of mesoporous silica core/yttria shell: a potential therapeutic agent for hepatic tumors

A new low-density silica core/yttria shell microspheres was developed for medical purposes. For preparing the core of this material, sol-emulsion-gel method was used. It was then calcined at 1,000 °C to increase the strength of the mesoporous beads. After cooling, it was added into a solution containing the mixture of yttrium chloride and urea. Under these circumstances, yttrium chloride can decompose to yttrium basic carbonate particles by the gradual hydrolysis of urea. These particles are able to deposit on the surface of mesoporous silica beads. Different coated samples were prepared under various pH, temperature and stirring conditions. Samples were heated to convert yttrium basic carbonate to yttria. The resulting silica core/yttria shell microspheres was characterized by laser diffractometer, scanning electron and optical microscopy techniques. It was found the pH of silica sols, aging time and Span-80 play important role in the stage of mesoporous bead preparation. Furthermore, the findings showed the heating of core/shell microspheres was essential for the ultimate strength of the shell. The in vitro chemical durability tests showed the release of yttrium ion in two simulated body fluids at pH 6 and 7 was negligible after 4 weeks.     

Preparation and characterization of low dispersity anionic multiresponsive core-shell polymer nanoparticles

We prepared anionic multistimuli responsive core-shell polymer nanoparticles with very low size dispersity. By using either acrylic acid (AA) or methacrylic acid (MA) as a comonomer in the poly(N-isopropyl acrylamide) (PNIPAM) shell, we are able to change the distribution of negative charges in the nanoparticle shell. The particle size, volume phase transition temperature, and aggregation state can be modulated using temperature, pH, or ionic strength, providing a very versatile platform for applications in sensors, medical diagnostics, environmental remediation, etc. The nanoparticles have a glassy poly(methyl methacrylate) (PMMA) core of ca. 40 nm radius and a cross-linked PNIPAM anionic shell with either AA or MA comonomers. The particles, p(N-AA) and p(MA-N), respectively, have the same total charge but different charge distributions. While the p(MA-N) particles have the negative charges preferentially distributed toward the inner shell, in the case of the p(N-AA) particles the charge extends more to the particle outer shell. The volume phase transition temperature (T(VPT)) of the particles is affected by the charge distribution and can be fine-tuned by controlling the electrostatic repulsion on the particle shell (using pH and ionic strength). By suppressing the particle charge we can also induce temperature-driven particle aggregation.     

Aggregation behavior of poly(N-isopropylacrylamide) microspheres

Electrophoretic mobility and aggregation in suspensions of three types of microspheres (Ms 1, Ms 2 and Ms 3) are studied at different pH, ionic strengths and temperatures of the medium. Here Ms 1 is a core particle composed of poly(N-isopropylacrylamide-co-styrene). Ms 2 is a core-shell microsphere consisting of Ms 1 as the particle core covered with a surface layer of poly(N-isopropylacrylamide) hydrogel. Ms 3 is also a core-shell microsphere composed of MS-1 covered with a surface layer of poly(N-isopropylacrylamide-co-acrylic acid) hydrogel. The charge density zN and the softness parameter 1/λ of the microspheres were obtained from the electrophoretic mobility data on the basis of an electrokinetic theory of soft particles. It is shown that when zN is large, suspensions of microspheres are always stable, showing no aggregation. When zN is small, the suspensions are stable for large 1/λ but show strong aggregation for small 1/λ.     

Effect of pH of aqueous ceramic suspensions on colloidal stability and precision of analytical measurements using slurry nebulization inductively coupled plasma atomic emission spectrometry

Colloidal stability of silicon nitride, silicon carbide and boron carbide aqueous slurries used for slurry nebulization inductively coupled plasma atomic emission spectrometry has been investigated in the pH range 2–10 by electrophoretic mobility and particle size measurements, together with sedimentation tests. The mean particle size of silicon nitride and silicon carbide suspensions change with increasing pH showing a maximum at the isoelectric points (pH 7.5 and 5.5 respectively). The particle size distribution of boron carbide slurries remains practically constant and the zeta potential of suspended boron carbide particles shows a small change in the pH range investigated. The silicon nitride and silicon carbide slurries have good stability at pH below 5 and above 8, respectively. Boron carbide slurries show excellent stability in the whole pH range investigated. The time demand for stabilization of the emission line intensities from the start of nebulization strongly depends on the colloidal stability of slurries. Consequently, it is advantageous to nebulize aqueous suspensions with a pH as far from the isoelectric point of the solid as possible and with the ionic strength of the dispersion medium as low as possible. The RSD values of the line intensity measurements determined after 3 min stabilization time decrease with increasing stability of the aqueous slurries.     

Interfacial and rheological properties of humic acid/hematite suspensions

This work deals with the effect of humic acid (HA) adsorption on the interfacial properties, the stability, and the rheology of aqueous iron oxide (hematite) suspensions. It is first of all demonstrated that HA effectively adsorbs onto hematite, mainly at acid pH. Since the charge of the HA chains is negative, it will be electrostatically attracted to the hematite surface below the point of zero charge of the particles, when they are positively charged. Electrophoresis measurements of hematite suspensions as a function of pH in the presence and absence of HA clearly demonstrate the adsorption of negatively charged entities on the oxide. Since the HA-covered particles can be thought of as "soft" colloids, Ohshima's theory was used to gain information on the surface potential and the charge density of the HA layer (H. Ohshima, in: A.V. Delgado (Ed.), Interfacial Electrokinetics and Electrophoresis, Dekker, New York, 2002, p. 123). A different procedure was also used to ascertain the degree of modification experienced by the hematite surface when placed in contact with HA solutions. The contact angles of selected liquids on pretreated hematite layers lead to the conclusion that the humic acid molecules impart to the particles a significant electron-donor character, in turn increasing their hydrophilicity. All this amount of information is used in the work for the interpretation of the rheological properties of hematite suspensions; the results are consistent with a stabilizing effect of HA adsorption on the suspensions, mainly as a consequence of the increased electrostatic repulsion between particles.     

Effect of pH and Salt on Rheological Properties of Aerosil Suspensions

Ionic strength and pH will influence the zeta potential of suspended particles, and consequently particle interactions and rheological properties as well. In this study the rheological properties and aggregation behaviour of Aerosil particles dispersed in aqueous solutions with various pH and salt concentration were studied. The potential energy was estimated by the DLVO theory and short range hydration forces and compared to the experimentally determined zeta potential. The strongest attraction between particles occurs at the isoelectric point (pH 4) and resulted in large aggregates, which gave relatively higher values of viscosity, yield stress, moduli, and shear thinning effects. The relative viscosity as a function of volume fraction was fitted to the Krieger and Dougherty model for all the suspensions. Oscillation measurements showed that the suspensions display elastic behaviour at low pH and viscous behavior at high pH. Furthermore, suspensions with high salt content had higher storage moduli. A power law dependency of storage moduli with volume fraction could be used to indicate the interaction strength between particles.     

Structural characterization of nanoparticles from thermoresponsive poly(N-isopropylacrylamide)-DNA conjugate

Poly(N-isopropylacrylamide) (PNIPAAm) grafted with single-stranded (ss) DNA conjugate (PNIPAAm-g-DNA) self-assembles above its lower critical solution temperature to form colloidal particles. When the ssDNA within the particle hybridizes with its complementary DNA, the particles aggregate above a certain threshold of salt concentration with drastically increased turbidity in solution. Detailed structural information of the particle was obtained mainly by small-angle X-ray scattering. The influence of copolymer composition on the morphology of particle and non-crosslinking aggregation was examined. The particle consists of hydrophobic PNIPAAm core surrounded by hydrophilic DNA strands. The increase in DNA fraction brought about a significant decrease in core size, whereas the shell thickness little changed and corresponded to the length of DNA. A structural model with a sticky potential was applied to the analysis of particle aggregate. This analysis provided that the particles aggregate while the coronal layers interpenetrate each other. The interaction between the particles was quantified in terms of the sticky potential and showed a trend to be influenced by the particle size rather than the graft density of DNA strands on the particle.     

A turbidimetric method to measure isoelectric points and particles deposition onto massive substrates

A simple experimental approach was developed to determine the adhesion rate of particles onto massive substrate. Turbidimetry measurements are used to follow the evolution of particle concentration in a suspension in dynamic contact with the walls of a vessel made of different materials. This method allows to rapidly obtain qualitative results about the adhesion of metallic oxides particles on massive substrates. Adhesion of particles of charged latex onto glass was used to validate the approach and was shown to be a method to determine isoelectric points (IEP) of massive substrates. Then, the adhesion of an iron oxide (hematite) particles onto several substrates was studied to determine the reactivity of current labware (glass, polypropylene) and on a metal (aluminum) commonly found in industrial fouling problems. Adhesion of hematite was found to be pH-dependant, and occurs only below ca. 6 (glass) or 7 (polypropylene), and above 7 (aluminum). DLVO calculations were performed to model the hematite/water/glass system and are consistent with the experimental results. Experiments at temperature 7–50 °C have shown an increasing of the adhesion rate from 7 to 40 °C, then a constant value until 50 °C.     

Spectrophotometric and flow ultramicroscopic study of the aggregation and sedimentation stability of aqueous dispersions of sulfate lignin in a pH range of 12.0–2.3

The aggregation and sedimentation stability of low-concentrated (10 mg/l) aqueous dispersions of sulfate lignin are studied by the spectrophotometry and flow ultramicroscopy methods in a wide pH range (12.0–2.3). Initial solution of sulfate lignin (pH 12.0) is shown to be a polydisperse system stable with respect to aggregation and sedimentation. As pH decreases up to 3.2, the sedimentation stability is retained, whereas a loss of aggregation stability resulting in an enlargement of initial fine particles invisible with a flow ultramicroscope and their transition into the visible size range are observed even at pH 11.0. In the course of time, the formed visible particles aggregate with a concomitant decrease in their total concentration. This process is even more pronounced at pH 10.0. At pH 2.3, the system loses its sedimentation and aggregation stability, and the visible particle concentration increases by tens of times compared to pH 12.0 then, the particles aggregate that results in a decrease in the total particle concentration. At any pH value, the systems studied are polydisperse that is most pronounced at pH 2.3.     

掺铝铁饼状α-Fe2O3微粒的制备及性能

采用液相催化相转化法, 以Fe(III)与Al(III)的共沉淀为前驱物合成了铁饼状α-Fe2O3微粒, 探讨了各种因素如铝离子的掺杂浓度、反应温度以及催化剂Fe(II)离子用量等对合成铁饼状α-Fe2O3微粒的影响, 并对产物进行了X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、电子衍射(ED)、X射线光电子能谱(XPS)等表征, 研究了样品的热稳定性及磁性能. 结果表明: 初始pH值为9, nFe(II)/nFe(III)≤0.04, nAl/nFe(III)＝0.14、反应温度为100～140 ℃时, 可制备出铁饼状α-Fe2O3微粒. 尽管铝和铁均为三价且二者的氧化物均具有刚玉结构, 但因二者离子半径的差异而使α-Fe2O3晶胞参数因铝取代铁而减小, 其矫顽力和剩磁也因铝取代而发生变化. 电子衍射证明该方法合成的微粒为单晶粒子, 且具有较好的热稳定性.     

Hematite nanoparticle monolayers on mica electrokinetic characteristics

Electrokinetic properties of α-Fe(2)O(3) (hematite) nanoparticle monolayers on mica were thoroughly characterized using the streaming potential method. Hematite suspensions were obtained by acidic hydrolysis of ferric chloride. The average size of particles (hydrodynamic diameter), determined by dynamic light scattering (DLS) and AFM, was 22nm (pH=5.5, I=10(-2)M). The hematite monolayers on mica were produced under diffusion-controlled transport from the suspensions of various bulk concentration. The monolayer coverage, quantitatively determined by AFM and SEM, was regulated within broad limits by adjusting the nanoparticle deposition time. This allowed one to uniquely express zeta potential of hematite monolayers, determined by the streaming potential measurements, in terms of the particle coverage. Such dependencies, obtained for various pH, were successfully interpreted in terms of the three-dimensional electrokinetic model. A universal calibrating graph was produced enabling one to determine hematite monolayer coverage from the measured value of the streaming potential. The influence of the ionic strength, varied between 10(-4) and 10(-2)M, on the zeta potential of hematite monolayers was also studied. Additionally, the stability of monolayers (desorption kinetics) was determined under in situ conditions using the streaming potential method. Our experimental data prove that it is feasible to produce uniform and stable hematite particle monolayers of well-controlled coverage. Such monolayers may find practical applications as universal substrates for protein immobilization (biosensors) and in electrocatalytic applications.     

Effect of a weak magnetic field on hematite sol in stationary and flowing systems

The effect of a weak magnetic field on the aggregation state and electrophoretic mobility of hematite sol was studied in flowing (dynamic) systems as a function of time and electrolyte concentration (0–60 mmol/dm³ KCl) and compared with the effect of the field in stationary (static) systems and flow in the absence of the field. During the entire treatment period, the pH remained almost constant (4.06–4.24). Conductance varied with KCl concentration, but except for minor fluctuations appeared to be unaffected by any form of treatment. While aggregation of hematite was observed during dynamic magnetic treatment (change in turbidity, scattered light intensity, and photon correlation spectroscopy), little effect on aggregation state was observed for the static systems or for the flowing systems in the absence of the field. Mobility also increased during the first 30 min of static and dynamic magnetic treatment. After longer treatment periods (90–120 min), the mobility decreased, but in almost all cases remained larger than in the case of untreated systems. Changes in both mobility and particle aggregation state also showed a significant dependence on electrolyte concentration. These effects are discussed in terms of a magnetohydrodynamic interaction between the magnetic field and the charged colloidal particles, which results only when the particles are made to pass rapidly through the field.