Dispersion and rheology of surfactant-mediated silver nanoparticle suspensions

Polycrystalline silver (Ag) nanoparticles were dispersed in solvent mixtures consisting of 2-butoxyethyl acetate (BCA) and diethylene glycol monoethyl ether acetate (CA) in a BCA:CA weight ratio of 5:1. Three commercially available polymeric surfactants were used, and the gravitational sedimentation, agglomerate-size distribution, isothermal adsorption, and rheological behavior of the nanoparticle suspensions were examined. One of the surfactants (hereafter termed 9250) was found effective in stabilizing the Ag nanoparticle suspensions. Both the adsorption isotherm and the Fourier transform infrared spectroscopy revealed the preferential adsorption of the 9250 surfactant molecules on the nanoparticle surface, forming a Langmuir-type monolayer adsorption in the given solvents so that a steric stabilization was rendered. An optimal surfactant concentration of 5 wt.% (in terms of the solids weight) was determined experimentally. In addition, the Ag suspensions with a broad range of solids concentration (? = 1-16 vol.%) showed a shear-thinning flow character over a shear-rate range from 1 to 4000 s⁻¹, revealing that an attractive interparticle interaction was operative. Relative viscosity (η_r) of the nanoparticle suspensions deviated from the linearity when ? was greater than ∼10 vol.%; at which, the attractive potential began to dominate the interparticle interactions. This η_r-? dependence was compared with various existing models and the (viscosity) predictive capability of the models was discussed.     

Facile synthesis of additive-assisted nano goethite powder and its application for fluoride remediation

The present article describes a novel synthesis route for nano-sized goethite (α-FeOOH) using hydrazine sulphate as an additive. The X-ray diffraction (XRD) peaks of synthesized powder matched well with those of α-FeOOH. Transmission electron microscopy (TEM) showed the particles of irregular shape in the range of 1–10 nm. Batch adsorption experiments for fluoride uptake were performed to study the influence of various experimental parameters such as contact time (10 min to 7 h), initial fluoride concentration (10–150 mg L⁻¹), pH (2–11.6) and the presence of competing anions. The time data fitted well to pseudo-second-order kinetic model. The fluoride removal passed through broad maxima in pH ranges of 6–8. High adsorption capacity of 59 mg g⁻¹ goethite was obtained. The isothermic data fitted well to Freundlich model. The presence of other ions namely chloride and sulphate adversely affected fluoride removal. Fluoride from contaminated water sample could be successfully brought down from 10.25 to 0.5 mg L⁻¹.     

Simultaneous detection of dopamine and ascorbic acid in urine using the H-point standard addition method

A highly sensitive H-point standard addition method (HPSAM) was investigated for identification of dopamine and ascorbic acid in some synthetic and pharmaceutical samples in an aqueous medium at pH 9.2 using a universal buffer. The most suitable wavelengths for dopamine and ascorbic acid detection are 260:271 nm and 248:270 nm respectively. Recovery values are between 99.0–101 %. Also, the effect of most common interferents was studied. Detection ranges for dopamine and ascorbic acid are 2·10^–6–5·10^–5 M and 6·10^–6–3·10^–5 M respectively with an RSD range between 1.3 and 2.0 %. The method was used to determine both reagents in real and synthesized samples.     

Structural, optical and electrical properties of cubic AlN films deposited by laser molecular beam epitaxy

Cubic AlN films were successfully deposited on TiN buffered Si (100) substrates by a laser molecular beam epitaxy (LMBE) technique, and their crystal structure and optical and electrical properties were studied. The results indicate that cubic AlN films show the NaCl-type structure with a (200) preferred orientation, and the lattice parameter is determined to be 0.4027 nm. The Fourier transform infrared (FTIR) pattern of the cubic AlN film displays sharp absorption peaks at 668 cm⁻¹ and 951 cm⁻¹, corresponding to the transverse and longitudinal optical vibration modes. Ellipsometric measurements evidence a refractive index of 1.66–1.71 and an extinction coefficient of about zero for the cubic AlN film in the visible range. Capacitance–voltage (C–V) traces of the metal–insulator–semiconductor (MIS) device exhibit that the cubic AlN film has a dielectric constant of 8.1, and hysteresis in the C–V traces indicates a significant number of charge traps in the film.     

Influence of pH on the preparation of dispersed Ag–TiO<Subscript>2</Subscript> nanocomposite

In this paper, data concerning the effect of pH on the morphology of Ag–TiO₂ nanocomposite during photodeposition of Ag on TiO₂ nanoparticles is reported. TiO₂ nanoparticles prepared by sol–gel method were coated with Ag by photodeposition from an aqueous solution of AgNO₃ at various pH levels ranging from 1 to 10 in a titania sol, under UV light. The as-prepared nanocomposite particles were characterized by UV–vis absorption spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and N₂ adsorption/desorption method at liquid nitrogen temperature (−196 °C) from Brunauer–Emmett–Teller (BET) measurements. It is shown that at a Ag loading of 1.25 wt.% on TiO₂, a high-surface area nanocomposite morphology corresponding to an average of one Ag nanoparticle per titania nanoparticle was achieved. The diameter of the titania crystallites/particles were in the range of 10–20 nm while the size of Ag particles attached to the larger titania particles were 3 ± 1 nm as deduced from crystallite size by XRD and particle size by TEM. Ag recovery by photo harvesting from the solution was nearly 100%. TEM micrographs revealed that Ag-coated TiO₂ nanoparticles showed a sharp increase in the degree of agglomeration for nanocomposites prepared at basic pH values, with a corresponding sharp decrease in BET surface area especially at pH > 9. The BET surface area of the Ag–TiO₂ nanoparticles was nearly constant at around a value of 140 m² g⁻¹ at all pH from 1–8 with an anomalous maximum of 164 m² g⁻¹ when prepared from a sol at pH of 4, and a sharp decrease to 78 m² g⁻¹ at pH of 10.     

Influence of fractal surface dimension on the dissolution process of sparingly soluble CaCO<Subscript>3</Subscript> microparticles

The dissolution process of sparingly soluble CaCO₃ microparticles and how the fractal surface dimension of the particles changes during dissolution is analyzed. The particles and the dissolution process are studied using scanning electron microscopy, X-ray diffraction, nitrogen adsorption, laser diffraction and conductance measurements. Ball milling of the particles is shown to maintain the particle crystallinity, and to introduce an increased fractal surface dimension in the 1–10 μm size range. Dissolution is found to increase the surface dimension of initially smooth particles and to maintain the fractal surface roughness of milled particles. The dissolution process increases the relative number of small particles (50 nm–1 μm) whereas the larger ones decrease in size. The solubility of the milled fractal particles was ∼1.8 times higher than that for the initially smooth ones. The presented findings show that developing methods for increasing the fractal surface roughness of particles should be of interest for improving the solubility of poorly soluble drug candidates.     

A photosensitive copolymer for the gate insulator of organic thin-film transistors

A novel cross-linkable copolymer for the gate insulators of organic thin-film transistors (OTFTs) was synthesized by free radical copolymerization with methyl methacrylate and ethylene methylacrylate cinnamoylate. Copolymers of molecular weights (Mn: 109200–160000 g mol⁻¹) and polydispersities (1.59–2.24) were characterized by FTIR and NMR. Spin-coated thin films had smooth surfaces with the root-mean-square (RMS) surface roughness of 0.23 nm, 0.41 nm, respectively, before and after UV irradiation. Exposure of the copolymers to UV light produced cross-linking of the polymeric chains that could be confirmed by comparing the FTIR and UV spectra recorded prior and after irradiation. Moreover, the vanadyl-phthalocyanine (VOPc) OTFTs with the photosensitive copolymer as gate insulator were fabricated and found to exhibit a carrier mobility of 0.25 cm²/V s, an on/off ratio of 10⁴.     

Synthesis of hydrophobic gold nanoclusters: growth mechanism study,luminescence property and catalytic application

One-pot synthesis of well dispersed, size-controlled gold nanoparticles with the average size of 10–15 nm and luminescent gold nanoclusters with average size of 1.7–2.0 nm were successfully achieved by thermal decomposition of gold organometallic precursor CH₃AuPPh₃ in the presence of thiol surfactants in o-xylene. Only difference between the preparations of two types of Au nanoparticles is the amount of thiol surfactant employed. The mechanistic study of formation of gold nanoparticles was carried out by analyzing the samples at different reaction time intervals and revealed that two-staged growth process was involved. The nanoclusters showed strong red emission with the maximum intensity at about 600 nm. The maximum room temperature photoluminescence quantum yield was measured as 1.2%. The catalytic ability of the Au nanoclusters to promote Suzuki–Miyaura coupling involving the C–C bond formation was also investigated.     

Aqueous phase-synthesized small CdSe quantum dots: adsorption layer structure and strong band-edge and surface trap emission

We synthesized, in aqueous solution at room temperature, small water-soluble CdSe quantum dots (QDs) with strong photoluminescence (PL) and then correlated the PL with their adsorption layer structure. For synthesizing the QDs, their initial synthesis condition was controlled to form small Cd-containing species capable of passivating dangling bonds on the CdSe core surface. Each CdSe QD (d ~ 2.5 nm) consisted of a CdSe core (d ~ 2.1 nm), a cysteine (cys)-ligand shell, and an adsorption layer composed of Cd–cys complexes (mainly CdL(-H)⁻, cys ≡ H₂L), cys (as L²⁻), Cd(OH)₂, and CdO _x (x ≥ 1). Our CdSe QDs showed strong blue band-edge PL as well as strong green surface trap PL. Their PL quantum yield (QY) of ~18% was unexpectedly high, considering their extremely small core size and their absence of any wide-bandgap inorganic shell. We attributed the QY to their adsorption layer species. The small weakly charged Cd–cys complex and the small neutral cadmium oxides in the adsorption layer could relatively readily diffuse into the unprotected surface sites on the core. These wide-bandgap species coalesced selectively on the unprotected surface sites with minimal spatial disturbance to the preexisting surface Cd-ligand coordination, and passivated them effectively. These decreased nonradiative recombination of the excitons significantly and thus led to the unexpectedly high QYs.     

Silica coating of Co–Pt alloy nanoparticles prepared in the presence of poly(vinylpyrrolidone)

This article describes a method for silica coating of Co–Pt alloy nanoparticles prepared in the presence of poly(vinylpyrrolidone) (PVP) as a stabilizer. The Co–Pt nanoparticles were prepared in an aqueous solution at 25–80 °C from CoCl₂ (3.0 × 10⁻⁴ M), H₂PtCl₆ (3.0 × 10⁻⁴ M), PVP (0–10 g/L), and NaBH₄ (4.8 × 10⁻³–2.4 × 10⁻² M). The silica coating was performed for the Co–Pt nanoparticle colloid containing the PVP ([Co] = [Pt] = 3.0 × 10⁻⁵ M) at 25 °C in (1/4) (v/v) water/ethanol solution with tetraethoxyorthosilicate (TEOS) (7.2 × 10⁻⁵–7.2 × 10⁻³ M) and ammonia (0.1–1.0 M). Silica particles, which had an average size of 43 nm and contained multiple cores of Co–Pt nanoparticles with a size of ca. 8 nm, were produced at 1.4 × 10⁻³ M TEOS and 0.5 M ammonia after the preparation of Co–Pt nanoparticles at 80 °C, 5 g/L PVP, and 2.4 × 10⁻² M NaBH₄. Their core particles were fcc Co–Pt alloy crystallites. Their saturation magnetization was 2.0-emu/g sample, and their coercive field was 12 Oe.     

Fractal structure of fullerite

We have obtained macroscopic fractal aggregates of fullerite ranging in size from 100 to 400 μm. The fractal structure of fullerite is formed by microscopic (30–100 nm) fullerite crystals in the presence of a temperature gradient under conditions of diffusion-limited aggregation. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 9, 684–685 (10 May 1998)     

Aggregate structure and crystallite size of platinum nanoparticles synthesized by ethanol reduction

Monodispersed platinum (Pt) nanoparticles were synthesized from reducing hydrated hydrogen hexachloroplatinic acid (H₂PtCl₆·nH₂O) with ethanol in the presence of polyvinylpyrrolidone (PVP) as a steric stabilizer. Concentration of both PVP and ethanol influenced the aggregate structure and crystallite size of the nanoparticles. When the molar ratio of monomeric unit of PVP to Pt, i.e., [PVP]/[Pt], was one, the synthesized Pt particles coagulated pronouncedly into an inter-connected particulate network or self-organized into spherical superstructures with an apparent diameter ranging from 60 to 80 nm, depending on the ethanol concentration. The geometry and structure of these complex aggregates were characterized by fractal analysis. Fractal dimensions of 2.13–2.23 in three dimensions were determined from the Richardson’s plot, which suggests that a reaction-limited cluster–cluster aggregation model (RCLA) was operative. The Pt colloids became apparently more stable when the [PVP]/[Pt] ratio was increased greater than 20. Crystallite size of the Pt nanoparticles was found to increase linearly with the ethanol concentration as the [PVP]/[Pt] was held at one. This suggests that the reduction rate of PtCl₆ ²⁻ ions in solution is critically important to the synthesized crystallite size.     

Light-emitting Si nanostructures formed in silica layers by irradiation with swift heavy ions

Thin SiO₂ layers were implanted with 140 keV Si ions to a dose of 10¹⁷ cm⁻². The samples were irradiated with 130 Mev Xe ions in the dose range of 3×10¹²–10¹⁴ cm⁻², either directly after implantation or after pre-annealing to form the embedded Si nanocrystals. In the as-implanted layers HREM revealed after Xe irradiations the 3–4 nm-size dark spots, whose number and size grew with increase in Xe dose. A photoluminescence band at 660–680 nm was observed in the layers with the intensity dependent on the Xe dose. It was found that passivation with hydrogen quenched that band and promoted emission at ∼780 nm, typical of Si nanocrystals. In spectra of pre-annealed layers strong ∼780 nm peak was observed initially. Under Xe bombardment its intensity fell, with subsequent appearance and growth of 660–680 nm band. The obtained results are interpreted as the emission at ∼660–680 nm belonging to the imperfect Si nanocrystals. It is concluded that electronic losses of Xe ions are mainly responsible for formation of new Si nanostructures in ion tracks, whereas elastic losses mainly introduce radiation defects, which quench the luminescence. Changes in the spectra with growth of Xe ion dose are accounted for by the difference in the diameters of Xe ion tracks and their displacement cascades.     

Catalytic reduction of organic dyes at gold nanoparticles impregnated silica materials: influence of functional groups and surfactants

Gold nanoparticles (Au NPs) in three different silica based sol–gel matrixes with and without surfactants are prepared. They are characterized by UV–vis absorbance and transmission electron microscopic (TEM) studies. The size and shape of Au NPs varied with the organo-functional group present in the sol–gel matrix. In the presence of mercaptopropyl functionalized organo-silica, large sized (200–280 nm) spherical Au NPs are formed whereas in the presence of aminopropyl functionalized organo-silica small sized (5–15 nm) Au NPs are formed inside the tube like organo-silica. Further, it is found that Au NPs act as efficient catalyst for the reduction of organic dyes. The catalytic rate constant is evaluated from the decrease in absorbance of the dye molecules. Presence of cationic or anionic surfactants greatly influences the catalytic reaction. The other factors like hydrophobicity of the organic dyes, complex formation of the dyes with anionic surfactants, repulsion between dyes and cationic surfactant, adsorption of dyes on the Au NPs also play important role on the reaction rate.     

Collective effects accompanying magnetization of two-dimensional lattices of nanosize magnetic particles

Collective effects arising in a two-dimensional lattice of nanosize magnetic particles as a result of the dipole interparticle interaction are investigated by Hall magnetometry. The experimental system consists of 10⁵ permalloy particles having a diameter of ∼40 nm and a height of ∼40 nm and forming a lattice with a rectangular unit cell (90 nm×180 nm). We attribute the characteristic features observed in the magnetization curves to quasi-one-dimensionality of the experimental lattice of particles and to the formation of solitons in chains of dipoles. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 6, 475–479 (25 September 1998)     

Nonlinear optical absorption and refraction in Ru, Pd, and Au nanoparticle suspensions

We present the results of studies of the nonlinear optical properties of Pd, Ru, and Au nanoparticles. We studied the nonlinear refraction and nonlinear absorption of suspensions of these nanoparticles at 1064-nm wavelength. A relatively strong nonlinear absorption of the Pd nanoparticles was observed in the case of 1064-nm, 50-ps pulses (β=2×10⁻⁹ m W⁻¹). The Ru and Pd nanoparticles showed weak negative nonlinear refraction (γ∼−(6–8)×10⁻¹⁶ m² W⁻¹) in this spectral range. In the case of the Au nanoparticles, a saturated absorption at 532 nm dominated over other nonlinear optical processes.     

Synthesis and characterization of Mg-doped ZnO hollow spheres

Mg-doped ZnO nanoparticles were synthesized by a simple chemical method at low temperature with Mg:Zn atomic ratio from 0 to 7%. The synthesis process is based on the hydrolysis of zinc acetate dihydrate and magnesium acetate tetrahydrate were heated under refluxing at 65 °C using methanol as a solvent. X-ray diffraction analysis reveals that the Mg-doped ZnO crystallizes in a wurtzite structure with crystal size of 5–12 nm. These nanocrystals self-aggregated themselves into hollow spheres of size of 800–1100 nm. High resolution transmission electron microscopy images show that each sphere is made up of numerous nanoparticles of average diameter 5–11 nm. The XRD patterns, SEM and TEM micrographs of doping of Mg in ZnO confirmed the formation of hollow spheres indicating that the Mg²⁺ is successfully substituted into the ZnO host structure of the Zn²⁺ site. Furthermore, the UV–Vis spectra and photoluminescence (PL) spectra of the ZnO nanoparticles were also investigated. The band gap of the nanoparticles can be tuned in the range of 3.36–3.55 eV by the use of the dopants.     

Encapsulation of iron nanoparticles in alginate biopolymer for trichloroethylene remediation

Nanoscale zero-valent iron (NZVI) particles (10–90 nm) were encapsulated in biodegradable calcium-alginate capsules for the first time for application in environmental remediation. Encapsulation is expected to offers distinct advances over entrapment. Trichloroethylene (TCE) degradation was 89–91% in 2 h, and the reaction followed pseudo first order kinetics for encapsulated NZVI systems with an observed reaction rate constant (k _obs) of 1.92–3.23 × 10⁻² min⁻¹ and a surface normalized reaction rate constant (k _sa) of 1.02–1.72 × 10⁻³ L m⁻² min⁻¹. TCE degradation reaction rates for encapsulated and bare NZVI were similar indicating no adverse affects of encapsulation on degradation kinetics. The shelf-life of encapsulated NZVI was found to be four months with little decrease in TCE removal efficiency.     

Au, Ge, and AuGe nanoparticles fabricated by laser ablation

A eutectic AuGe target immersed in distilled water was ablated by pulsed ultraviolet laser light. The structure of the ablated material was investigated by high-resolution transmission electron microscopy (HRTEM). The images show formation of nanowire structures of AuGe up to 100 nm in length, with widths of 5–10 nm. These nanostructures have Ge content significantly lower than the target material. Electron diffraction demonstrates that they crystallize in the α-AuGe structure. For comparison, laser ablation of pure Au and pure Ge targets was also performed under the same conditions. HRTEM shows that Ge forms spherical nanoparticles with a characteristic size of ~30 nm. Au forms spherical nanoparticles with diameters of ~10 nm. Similar to AuGe, it also forms chainlike structures with substantially lower aspect ratio.     

The synthesis of hafnium nanomaterials by alkali metal reduction of hafnium tetrachloride

Hafnium tetrachloride was reduced in organic solvents with lithium powder, sodium–potassium alloy, or lithium hydride/Et₃B. All reductions required sonochemical agitation to proceed at an appreciable rate, with the notable exception of the reaction of HfCl₄ with Li in diethyl ether. Activation of C–H bonds occurred in all reactions, which resulted in carbon-containing products. HfCl₄ was reduced on a 50-g scale with LiH/Et₃B, and a 10-g scale with Li powder in pentane. All the solid products from the reductions were converted to nanomaterials by annealing under vacuum from 500 to 1,000 °C, which also resulted in the sublimation of the alkali metal salts. The nanomaterials contain a mixture of products with the α-Hf (hexagonal) structure (crystallite size 8–250 nm) and the HfC (FCC) structure (crystallite size 3–80 nm), with the amount of hafnium in the bulk annealed product varying from 88 to 99 wt%. When toluene, pentane, or triethylamine solvents were used, the presence of amorphous graphitic or carbonaceous material was also detected by solid state ¹³C NMR. Thermally annealed products were additionally characterized by electron microscopy and thermal analysis under Ar/O₂, and have BET surface areas ranging from 2.7 to 155 m²/g.