Stable Nanoparticle Suspensions Research Articles

The influence of dispersing and stabilizing of indium tin oxide nanoparticles upon the characteristic properties of thin films

Stable suspensions of indium tin oxide nanoparticles were prepared by dispersing for 1 h in ethanol and stabilizing with 2-[2-(2-Methoxyethoxy)ethoxy]acetic acid. Particle size, morphology, and structure were characterized by a combination of dynamic light scattering, high resolution transmission electron microscopy, and X-ray diffraction. Spin coating of the stable suspensions resulted in densely packed films with a high transparency. Dispersing times exceeding 1 h led to a significant “overdispersing” effect, i.e. an increasing aggregate size of the suspensions was observed. Zeta-potential, pH, and X-ray photoelectron spectroscopy measurements were conducted to achieve a detailed understanding of the effect of “overdispersing”. With an increasing time of dispersion, i.e. with a decreasing stability of the suspensions, the thin films fabricated by spin coating displayed an increasing pore size distribution and surface roughness. In addition a strong decrease in transmittance and in conductivity was observed.

A simple route to prepare stable hydroxyapatite nanoparticles suspension

A simple ultrasound assisted precipitation method with addition of glycosaminoglycans (GAGs) is proposed to prepare stable hydroxyapatite (HAP) nanoparticles suspension from the mixture of Ca(H2PO4)2 solution and Ca(OH)2 solution. The product was characterized by XRD, FT-IR, TEM, HRTEM and particle size, and zeta potential analyzer. TEM observation shows that the suspension is composed of 10–20 nm × 20–50 nm short rod-like and 10–30 nm similar spherical HAP nanoparticles. The number-averaged particle size of stable suspension is about 30 nm between 11.6 and 110.5 nm and the zeta potential is −60.9 mV. The increase of stability of HAP nanoparticles suspension mainly depends on the electrostatic effect and steric effect of GAGs. The HAP nanoparticles can be easily transported into the cancer cells and exhibit good potential as gene or drug carrier system.

Intrinsically stable dispersions of silicon nanoparticles

Stable suspensions of silicon nanoparticles (SiNP) were fabricated by dispersion in 1-butanol as well as ethanol without the application of an additive. In order to achieve an in-depth insight into the stabilizing mechanism, the particle–particle interactions need to be considered. In this respect the total interaction energy of the silicon nanoparticles in 1-butanol and ethanol was calculated for three model systems according to the DLVO theory: (1) two solid silicon spheres, (2) two spheres with a silicon core and an amorphous silicon dioxide shell, and (3) two spheres with a silicon core, an amorphous silicon dioxide shell and a monolayer of adsorbed solvent molecules. The results of the calculations are evaluated and discussed with regard to experimental data obtained by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), high resolution transmission electron microscopy (HRTEM), and zeta potential measurements.

Preparation and properties of water-based magnetic fluids

Stable suspensions of superparamagnetic iron oxide nanoparticles in water (water-basedferrofluids) were prepared using citric acid (CA) as a surfactant. The influences of differentfactors on the amount of nanoparticles in a stable suspension were systematically studied.These factors, including the temperature, the pH value and the concentration of CAapplied during the adsorption of the CA onto the nanoparticles and during their suspensionin water, were evaluated. The highest content of nanoparticles in a stable suspensionwas obtained when the CA was absorbed at pH values of around 5.2, where twocarboxyl groups are dissociated, and when the nanoparticles were suspended at a pHof around 10, where all three carboxyl groups of the CA are in a dissociatedstate.

Preparation of stable suspensions of gold nanoparticles in water by sonoelectrochemistry

Stable suspensions of gold nanoparticles in water were prepared with high yield by a novel one-step ultrasound assisted electrochemical process. Various strategies based on the addition of either tailor-made polymers or mixtures of commercially available polymers, in the electrochemical bath have been found successful to avoid nanoparticles aggregation commonly observed by sonoelectrochemistry. α-Methoxy-ω-mercapto-poly(ethylene oxide) or poly(vinyl pyrrolidone)/polyethylene oxide mixtures were able to build up a coalescence barrier around the gold nanoparticles. The results showed that the size of the gold nanoparticles could be easily tuned between 5 nm and 35 nm by simple control of the electrochemical parameters, i.e. the deposition time ( T ON) from 10 ms to 20 ms. The properties of as-prepared gold nanoparticles were compared to the ones of gold colloids prepared by the more conventional wet nanoprecipitation method using chemical reductive agents.

Fabrication of resistive CO gas sensor based on SnO2 nanopowders via low frequency AC electrophoretic deposition

A resistive CO gas sensor has been fabricated using AC electrophoretic deposition (ACEPD) technique. SnO2 thick films are deposited by applying low frequency (0.01–1,000 Hz) AC electric field to a stable suspension of SnO2 nanoparticles in acetyl acetone. A carbon film base electrode is used as deposit substrate. Effect of CO gas exposure on conductivity of the SnO2 film at 300 °C is investigated. Results show that the sensor is sensitive and its response is repeatable. This work shows that ACEPD can be used as an easy and cheap technique for fabrication of electronic devices such as ceramic gas sensors.

Stabilized polymeric nanoparticles for controlled and efficient release of bifenthrin

Nanoparticle formulations of pesticides have been proposed to produce a better spatial distribution of the pesticide on leaf surfaces, which provides better efficiency. Nanoparticles are well studied for drug delivery and sustained release but not in the agricultural sciences, because of the difficulty in generating stable pesticide nanoparticles with controlled particle size distribution and because the processes to generate nanoparticles are usually costly. In this paper, a model pesticide, bifenthrin, has been prepared in nanoparticle form by using the Flash NanoPrecipitation process. The process involves rapid micromixing to effect supersaturation, and polymer assembly to control particle size. A multi-inlet vortex mixer (MIVM) was developed to provide rapid micromixing, high supersaturation and rapid nucleation and growth of bifenthrin nanoparticles. Several polymeric stabilizers were tested. With an increase in pesticide loading from 50 to 91%, nanoparticle size increased from 100 to 200 nm. The stability of the nanoparticle dispersions was followed for more than 12 days. The steric stability caused by the corona structure of the hydrophilic block of the polymers prevents nanoparticles aggregation. Ostwald ripening is responsible for the slow particle size growth observed. Flash NanoPrecipitation using an MIVM provides a cost-effective process to produce stable pesticide nanoparticle suspensions. Nanoparticle size depends on supersaturation, pesticide loading and type of polymer. Nanoparticle pesticides potentially provide higher efficiency, better uniformity of coverage for highly active compounds and less exposure to workers, relative to compounds solubilized in organic solvents.

Shear Flow of Aggregated Nanosuspensions–Fundamentals and Model Formulation

Theoretical aspects of shear flows of aggregated nanosuspensions are presented and applied to formulate appropriate models. Technological context of this work is related to formulation of stable suspensions of nanoparticles of specific rheological properties by breaking‐up nanoparticle clusters in high shear devices. Accordingly the population balance modeling is applied with kinetics including effects of aggregation, breakage and restructuring of aggregates; effects of suspension rheology on the flow are included as well. Rheological model includes the effect of clustering of primary nanoparticles. Population balances are solved using QMOM that is linked to the CFD code. Results of numerical simulations are presented for laminar and turbulent flows. Part of the 1st International Conference on Industrial Processes for Nano and Micro Products, London, 2007.

Formation and stabilization of submicron particles via rapid expansion processes

Submicron particles were produced by rapid expansion of supercritical solution into air (RESS) or an aqueous surfactant solution (RESSAS) to minimize particle growth and to prevent particle agglomeration. Thereby the effect of process conditions on the size of the particles precipitated was investigated. The obtained product was evaluated by measuring particle size by 3-wavelength extinction measurements, dynamic light scattering, specific surface areas by nitrogen gas adsorption, melting behaviour by differential scanning calorimetry, particle morphology by X-ray diffraction, scanning electron micrographs (SEM), and drug loading by high performance liquid chromatography. Prior to the particle formation experiments, the melting temperature of Salicylic acid under CO 2 pressure and the solubility of Salicylic acid in CO 2 were measured. The size of Salicylic acid particles produced via RESS decreased from 230 to 130 nm as the pre-expansion temperature decreased from 388 to 328 K and the specific surface area of the micronized particles was found to be up to 60 times higher than that of the unprocessed material. RESSAS experiments demonstrate that in 1 wt.% Tween 80 solutions Salicylic acid concentrations of 4.6 g/dm 3 could be stabilized with particle diameters in the range of 180 nm. Additional experiments show that Ibuprofen nanoparticles with an average size of 80 nm and a drug concentration of 2.4 g/dm 3 could be stabilized in 1 wt.% Tween ® 80 solutions. The use of a SDS solution instead of Tween ® 80 results in a stable aqueous suspension of phytosterol nanoparticles, where the average particle size is 50 nm at a drug concentration of 5.6 g/dm 3.

Synthesis and functionalization of magnetite nanoparticles with aminopropylsilane and carboxymethyldextran

Magnetite nanoparticles were functionalized with carboxymethyldextran (CMDx) covalently attached to the particles to prevent polymer desorption in biomedical applications. Carbodiimide chemistry was used to react carboxylic groups (–COOH) present in the CMDx molecule with amine end groups (NH2) previously grafted onto the nanoparticle surface by condensation of aminopropylsilane (APS) molecules. This method produces highly stable suspensions of magnetite nanoparticles with electrostatic and steric repulsion and no particle precipitation in the presence of electrolytes.

Synthesis and characterisation of monodispersed silver nanoparticles with controlled size ranges

A method that enables reproducible synthesis of low aspect ratio, monodispersed and stable silver nanoparticle suspensions, uniform in its optical response and tunable over a range of diameters has been developed. The uniformity of the nanoparticles has been accurately determined using electron and atomic force microscopies for diameters down to 50 nm. These particles are highly suited to applications in optical nanotechnology.

Mechanism of enhancement/deterioration of boiling heat transfer using stable nanoparticle suspensions over vertical tubes

Boiling heat transfer using nanofluids has been a subject of a few investigations in the past few years and incongruous results have been reported in literature regarding the same. Conflicting explanations for deterioration of pool boiling heat transfer coefficient at higher concentrations (4–16wt%) have been presented by various researchers. Recently, a few works have reported a significant enhancement in pool boiling heat transfer coefficient at lower concentrations (0.32–1.25wt%) and the physical reasons for this have not been explained. The present work is aimed at removing these ambiguities. Experiments have been carried out by using stable water based nanofluids containing alumina nanoparticles (average sizes of 47 and 150nm) with vertical tubular heaters of various surface roughnesses (48, 98, and 524nm). It has been observed that with the rough heater (Ra=524nm), heat transfer is significantly enhanced and the enhancement reaches ∼70% at a particle loading of 0.5wt%. With the smooth heater (Ra=48nm), heat transfer is significantly deteriorated and the heat flux reduction reaches ∼45% at a particle loading of 2wt%. Further, it has been observed that a parameter which is the ratio of average size of the particle to the average roughness value of the heater can explain the reported controversy in the pool boiling behavior of these suspensions.

Control of the Morphology and Particle Size of Boehmite Nanoparticles Synthesized under Hydrothermal Conditions

The spontaneous nucleation under hydrothermal conditions often leads to aggregation of crystallizing particles, which is an undesired phenomenon when the goal is the preparation of nanocrystals with narrow particle size distribution. The present paper reports on the synthesis of boehmite nanocrystals under hydrothermal conditions. An aqueous aluminum chloride salt solution was first prepared, and the pH was increased to 11 using a 5 M sodium hydroxide solution. The hydrothermal treatment was performed at 160 degrees C for different periods of time. The system yielded relatively small (15-40 nm) boehmite crystallites aggregated into larger (160 nm) particles. To avoid the aggregation, a biocompatible polymer, sodium polyacrylate (NaPa) 2100, was employed as a size-/morphology-controlling agent. Thus, stable colloidal suspensions of rounded boehmite nanoparticles having a size between 15 and 40 nm were obtained at 160 degrees C for 24 h. Further, the effect of synthesis time on the morphological features of boehmite synthesized in such a NaPa-containing system was investigated. The increase of the synthesis time from 24 to 168 h resulted in the formation of very long boehmite fibers (1000-2000 nm) with an average diameter of about 10 nm. The boehmite samples were characterized by XRD, DLS, TEM, IR, N2 adsorption, and zeta potential measurements. The colloidal stability of the obtained suspension was also studied.

Dispersing silicon nanoparticles in a stirred media mill – investigating the evolution of morphology, structure and oxide formation

AbstractSilicon nanoparticles were dispersed for 24 hours in 1‐butanol using a stirred media mill. Via this process intrinsically stable suspensions (in regard to aggregation) of Si nanoparticles were produced after 6 hours of dispersing. The evolution of morphology, particle size and structure was investigated by dynamic light scattering, X‐ray diffraction, Raman spectroscopy and high resolution transmission electron microscopy as a function of dispersing time. The average crystallite size decreased from about 18 nm down to about 10 nm within 24 hours of milling as determined by X‐ray diffraction and Raman scattering measurements. In addition careful analysis of the Raman spectra revealed a decrease of the crystalline volume fraction from 75% down to 24% and a corresponding increase of the amorphous phase. The microstructural development with varying crystallite size and crystalline volume fraction was directly confirmed by transmission electron microscopy measurements. Elemental analysis showed an increase of oxygen content that was directly proportional to the increase in specific surface area of the silicon nanoparticles during the dispersing process. The surface chemistry of the Si nanoparticles was analyzed by diffuse reflectance infrared Fourier transform spectroscopy that indicated vibrational bands of HSi–Si3–x Ox , SiOx , and residual 1‐butanol. The final product of the dispersing process seems to be a two‐phase mixture of amorphous Si and Si nanocrystallites covered with SiOx on the surface. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Dimensional analysis of aqueous magnetic fluids

A comparison of the synthesis and characterization of three aqueous magnetic fluids intended for biomedical applications is presented. Stable colloidal suspensions of iron oxide nanoparticles were prepared by a co-precipitation method with the magnetite cores being coated with β-cyclodextrin, tetramethylammonium hydroxide and citric acid. Rheological properties of the fluids were investigated, i.e. viscosity (capillary method) and surface tension (stalagmometric method) in correlation with their density (picnometric method). The dimensional distributions of the ferrophase particles physical diameter of these three magnetic fluids – revealed on the basis of transmission electron microscopy (TEM) data – as well as the diameter distributions of some other magnetic fluids presented in the literature, were comparatively analyzed using the box-plot statistical method. In order to extract complementary data on the magnetic diameter of an iron oxide core, magnetization measurements as well as X-ray diffraction pattern analysis were carried out. Interpretation of all the measurement data was accomplished by assessing the suitability of the three magnetic fluid samples from the viewpoint of their stability and biocompatibility.

Preparation of highly concentrated and stable suspensions of silver nanoparticles by an organic base catalyzed reduction reaction

Highly concentrated and stable suspensions of silver nanoparticles have been synthesized by chemical reduction from silver nitrate in a formaldehyde reductant using an organic base, triethylamine, as the reaction promoter. In this reaction, a low molecular weight organic compound, thiosalicylic acid (TSA), was used as the protecting agent. The average size of the silver nanoparticles prepared from this method was less than 10 nm, which allowed low-temperature sintering of the metal. The suspensions were further stabilized by the addition of excessive triethylamine, which forms an amine salt with TSA. A 50 wt%, stable suspension has been prepared. The suspensions of silver nanoparticles prepared by this method are free from any metal ion contamination, and are suitable for use in semiconductor industries.

Uptake and Biocompatibility of Functionalized Poly(vinylalcohol) Coated Superparamagnetic Maghemite Nanoparticles by Synoviocytes In Vitro

Superparamagnetic iron oxide nanoparticles (SPION) were coated with either Polyvinyl alcohol (PVA) or Vinyl alcohol/vinyl amine copolymer and further functionalized with the fluorochromes Cy3.5 or Texas Red. A colloidally stable suspension of nanoparticles was incubated on sheep synovial cells in vitro for 3, 24, 72, and 120 hours. Nanoparticle internalization into synoviocytes as well as biocompatibility was visualized using light, fluorescence and confocal microscopy and fluorochrome labeled cells were quantified by flow cytometry. Data were analyzed by ANOVA factorial tests. Amino-PVA-SPION alone was detectable in cytoplasmic endosome-like structures after 3 hours of incubation but resulted in early cell death after 24 hours. Although amino-PVA-Cy3.5-SPION and PVA-TexasRed-SPION were taken up more slowly and less intensely, both labeled more than 80% of the cells in culture, but did not significantly change cell morphology or vitality at any time of evaluation in comparison to control cells. Results indicate that functionalized amino PVA-coated SPION are biocompatible, were successfully internalized by synoviocytes and hold promise for future biomedical applications utilizing magnetic drug targeting in joint disease.

Stochastic probability modeling to predict the environmental stability of nanoparticles in aqueous suspension

The term "nanomaterial" describes a preparation in which the particle size is on the order of 10 to 100 nm in diameter. Such particles have the ability to form suspensions in fluid media such as air and water that can dramatically increase the environmental transport potential in comparision with like materials of larger particle sizes. Quantifying such transport requires an ability to predict the stability of such suspensions as to their tendency to aggregate or interact with other environmental constituents. In this paper, we present a method for predicting the magnitude and uncertainty associated with nanoparticle suspension stability. The critical buoyancy properties are predicted using the Boltzmann equation. The rates of aggregation are then predicted on the basis of molecular collision and adhesion coefficients. The progress of particle growth is simulated across all potential pathways probabalistically using the Gillespie model to characterize the uncertainty. Discussion is provided regarding potential environmental applications and further potential development in predicting particle behavior and effects on the environment.

Nanoparticle aggregation influenced by magnetic fields

Colloidally stable nanoparticle suspensions of iron hydroxide FeO(OH) at pH 2 have been prepared and shown to be non-magnetic. However, when the pH of the dispersion was raised to destabilise the suspension, aggregates near 200 nm diameter were detected by Photon Correlation Spectroscopy (PCS), and these were influenced by magnetic fields in the 50 kA m −1 range. These aggregates were unusual in that they were colloidally stable and did not behave as flocs. Consequently they were called nucleags to distinguish them from conventional flocculated agglomerates. As the pH was raised further towards the isoelectric point, flocculation of the nanoparticles was observed and brown sludge deposited on the base of the container. This material was not influenced by magnetic fields. A preliminary theory has been proposed to account for the observations. The experimental results fitted the curve with a one parameter adjustment. The conclusion was that magnetic fields can influence the behaviour of metastable aggregates in nanoparticle dispersions under certain colloidal conditions. The results may be relevant to deposition of scaling or fouling films in pipes carrying fluids.

Understanding the differences between microporous and mesoporous synthesis through the phase behavior of silica

The link between M41S mesoporous silicates and all-silica zeolites during the initial stages of synthesis is analyzed with small-angle scattering and conductivity experiments. The phase behavior of silica in aqueous solutions is studied for a family of quaternary ammonium hydroxides, from tetramethylammonium to dodecyltrimethylammonium. All solutions exhibit a critical aggregation concentration at a 1:1 SiO 2:[OH −] initial molar ratio with solutions containing short chain compounds forming optically transparent (clear) nanoparticle suspensions, and solutions of long chain compounds phase separating into a solid and a liquid phase. The solid phase is analyzed with X-ray diffraction and thermogravimetric analysis and is found to have a hexagonal structure similar to MCM-41. Mid-sized chain length compounds form solutions containing both the phase separated solid and nanoparticles. In addition to studying phase behavior, the role of attractive hydrophobic interactions is studied using water/ethanol solutions. In ethanolic solutions, the entire family of quarternary ammonium compounds are found to form stable nanoparticle suspensions.