Transport of engineered nanoparticles in saturated porous media

Engineered nanoparticles (NPs) can be released into soils as emerging groundwater contaminants because many of them show toxic effects to the ecosystems; however, their fate and transport in soils are largely unknown. The present work examined the transport behavior of two NPs, silver nanoparticles (AgNPs) and carbon nanotubes (CNTs), in saturated porous media. Sodium dodecylbenzene sulfonate (SDBS), an anionic surfactant, was used to disperse the engineered NPs to enhance their stabilities in water. The solubilized NPs were then applied to laboratory columns packed with two types of water-saturated quartz sand to obtain their breakthrough curves. The experimental results showed that the surfactant-solubilized NPs were highly mobile in the saturated porous media. The transport of CNTs in the column was similar to that of colloidal montmorillonite and their recovery rates were around 100%. Less than 15% of the AgNPs were retained in the saturated column during the breakthrough experiments. However, most of the retained AgNPs were released when a SDBS-free water pulse was used to flush the sand column. The Derjaguin–Landau–Verwey–Overbeek (DLVO) theory and a colloid transport model were used to simulate the fate and transport of the engineered NPs in the sand columns. The DLVO theory worked well with AgNPs, but failed to represent the interactions between CNTs and the two sand media. Predictions of the transport model matched the experimental breakthrough data of the two engineered NPs well. Our results indicate that theories and models of colloid transport in porous media may be applicable to describe the fate and behavior of engineered NPs under certain circumstances.     

Electrochemical characterization of core@shell CoFe2O4/Au composite

Quantum dots (QDs) have received considerable attention due to their unique optical and electrical properties. Although substantial research has focused on the potential applications and toxicological impacts of QDs, far less effort has been directed toward understanding their fate and transport in the environment. In this work, the effect of four coatings, polyethylene glycol functionalized polymer (PEGP), carboxyl derivatized polymer (COOHP), linoleic acid (LA), and polyacrylic acid-octylamine (PAA-OA), on the transport and retention of QDs in porous media were evaluated under environmentally relevant conditions. Aqueous QD suspensions (ca. 10 nM) were introduced into water-saturated columns packed with 40–50 mesh Ottawa sand at a pore-water velocity of 7.6 m/day. At an ionic strength (IS) of 3 mM and pH of 7, PEGP-coated QDs were completely retained within the column, while more than 60 % of COOHP-coated QDs were transported through a column run under identical conditions. When PAA-OA and LA were used as coatings, effluent QD recoveries increased to more than 65 and 89 % of the injected mass, respectively. Additionally, a decrease in pH from 9.5 to 5.0, or an increase of IS from 0 to 30 mM reduced the eluted mass of PAA-OA-coated QDs by more than 2 and 15 times, respectively. The relative mobility of coated QDs (LA > PAA-OA > COOHP > PEGP) was consistent with total interaction energy profiles between QDs and sand surfaces calculated based on Derjaguin–Landau–Verwey–Overbeek (DLVO) theory. At an IS of 3 mM (NaCl) and pH 7, a linear correlation was obtained between the fraction of eluted QDs and the magnitude of the primary interaction energy barrier. These findings demonstrate the strong dependence of QD transport on coating type and indicate that interaction energies based on DLVO theory can be used to predict the relative mobility of QDs in porous media.     

Heavy-metal distribution in pore waters of the Cona Marsh: A preliminary investigation on surface sediments

Summary The results of an investigation about the heavy-metal distribution in pore waters of an estuarine shallow-water system (Cona Marsh, Venice Lagoon) are described. The area was sampled for surface and subsurface sediments; pore waters were extracted by centrifugation and heavy-metal concentration measured by means of PIXE technique. A high variability of heavy-metal concentration was observed in pore waters of sampled sites, as a result of physico-chemical conditions in the water sediment column, with a different spatial distribution between two groups of metals (Fe, Mn and Crvs. Cu, Ni and Zn). Concentration gradients between pore and bottom waters were evaluated in order to investigate the metal enrichment as a function of their mobility in the sediment and diagenesis phenomena. Paper presented at the IX Congresso del Gruppo Nazionale per la Fisica dell'Atmosfera e dell'Oceano, June 8–10, 1992, Rome.     

Transport of surface-modified iron nanoparticle in porous media and application to arsenic(III) remediation

The surface-modified iron nanoparticles (S-INP) were synthesized, characterized and tested for the remediation of arsenite (As(III)), a well known toxic groundwater contaminant of concern. The S-INP material was fully dispersed in the aqueous phase with a particle size distribution of 2–10 nm estimated from high-resolution transmission electron microscopy (HR-TEM). X-ray photoelectron spectroscopy (XPS) revealed that an Fe(III) oxide surface film was present on S-INP in addition to the bulk zero-valent Fe⁰ oxidation state. Transport of S-INP through porous media packed in 10 cm length column showed particle breakthroughs of 22.1, 47.4 and 60 pore volumes in glass beads, unbaked sand, and baked sand, respectively. Un-modified INP was immobile and aggregated on porous media surfaces in the column inlet area. Results using S-INP pretreated 10 cm sand-packed columns containing ∼2 g of S-INP showed that 100 % of As(III) was removed from influent solutions (flow rate 1.8 mL min⁻¹) containing 0.2, 0.5 and 1.0 mg L⁻¹ As(III) for 9, 7 and 4 days providing 23.3, 20.7 and 10.4 L of arsenic free water, respectively. In addition, it was found that 100% of As(III) in 0.5 mg/L solution (flow rate 1.8 mL min⁻¹) was removed by S-INP pretreated 50 cm sand packed column containing 12 g of S-INP for more than 2.5 months providing 194.4 L of arsenic free water. Field emission scanning electron microscopy (FE-SEM) showed S-INP had transformed to elongated, rod-like shaped corrosion product particles after reaction with As(III) in the presence of sand. These results suggest that S-INP has great potential to be used as a mobile, injectable reactive material for in-situ sandy groundwater aquifer treatment of As(III).     

NMR investigation of water and methanol mobility in nanocomposite fuel cell membranes

Water and methanol transport behavior, morphology, and solvent adsorption of filler-free Nafion membrane, Nafion–SiO₂, Nafion–TiO₂, and two Nafion–Zr(HPO₄)₂ composites were investigated using nuclear magnetic resonance methods, including spin-lattice relaxation and pulsed-field-gradient spin-echo diffusion conducted under both variable temperature and variable hydrostatic pressure conditions and scanning electron microscopy analysis. A comparison between water and methanol self-diffusion coefficients reveals that the water mobility is higher than the methanol mobility in all the membranes. Additionally, the inclusion of inorganic fillers improves both the solvent uptakes and the transport properties of the composite membranes relative to filler-free Nafion, with the exception of one of the Nafion–Zr(HPO₄)₂ composite. Nafion–Zr(HPO₄)₂ composites were prepared by two different procedures, in situ and ex situ. Although phosphorus-31 magic-angle spinning nuclear magnetic resonance spectra show the same structures of the particles in both kinds of membranes, the morphology, solvent absorption properties, and solvent mobilities are very different. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur Mer, Sept. 9–15, 2007.     

Effect of mixed cations in synergizing the performance characteristics of PVA-based polymer electrolytes for novel category Zn/AgO polymer batteries—a preliminary study

Thin films of polymer electrolytes comprising of PVA and KOH (A) with and without the addition of zinc salts, viz., zinc acetate (B) and zinc triflate (C) as mixed cations were prepared via. solution casting method. The thermal stability and ionic conductivity of PVA–KOH solid polymer electrolyte (A) were improved by the partial substitution of KOH with zinc salts. Among the two salts, zinc triflate was found to improve both the physical as well as electrochemical properties of the PVA–KOH films more significantly than zinc acetate. An attempt to optimize the ratio of various components of polymer electrolytes, viz., polymer: KOH: zinc salt was also made, based on the dimensional stability and ionic conductivity values. Finally, the select category polymer film containing PVA–KOH–zinc triflate (C) in an optimum ratio of 40:35:25 was deployed in coin cell fabrication and subjected to charge–discharge studies with a view to demonstrate the possible electrochemical reversibility characteristics. Based on the encouraging results obtained from the cycling study, C type films [PVA–KOH–zinc triflate] qualify themselves as potential polymer electrolytes for use in rechargeable Zn/AgO polymer batteries.     

Electrically controllable metal–insulator-like transition in nanoparticle compacts

We report on the observations of tunneling transport in nanocompacts, where nanoparticles are packed into compact units using selective mass compositions and packing densities. An insulator-like thermal behavior in electron transport is seen in a very loosely packed 6-nm Ag nanocompact, whereas the densely packed 4.5-nm Au nanocompact displays a metal-like thermal behavior. Metal–insulator-like transitions, with the transition temperature can readily be tuned by controlling the bias voltage, are observed in the nanocompact consists of mixtures of 2.4 nm Ag and 4.8 nm core/shell Cu/Cu₂O nanoparticles. The resistivity across the metal–insulator transition is found to change by more than four orders-of-magnitude. At low bias voltages or small excitation currents, the metal–insulator transition occurs at ~190 K. The transition temperature can be tuned to reach the ambient temperature when a higher bias voltage or a larger current is allowed. Possible mechanisms that may produce the observed transport characteristics in the nanocompacts are discussed.     

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.     

Syntheses and pH sensing applications of imine-coupled phenol and polyphenol species derived from 2-amino-4-nitrophenol

Developing of new generation optical polymeric pH sensors has increasing importance due to their stable structures. Available polymeric sensors for different pH ranges are already needed. In the present study new kinds of monomeric and polymeric absorption pH sensors (HBANP and PHBANP) derived from 2-amino-4-nitrophenol were prepared. The novel sensors were investigated in various pH values using spectrophotometric, spectrofluorometric, and electrochemical techniques. The sensors showed sigmoidal correlations vs. pH range in optical measurements. These correlations were improved as mathematical formula to obtain the solution pH. HBANP and PHBANP differed from each other by response fields. HBANP had a sharp absorption increase between the pH of 6.5→7.5 while PHBANP spectrophotometrically responded at lower pHs. HBANP was colorless in acidic pHs, yellow-colored in neutral media and red-colored in alkaline pHs. With its colorimetric responses in various pHs HBANP can be used to develop color-tunable pH sensors. Electrochemical oxidation peak potentials and currents also particularly changed in various pHs.     

The characterization of electroplex generated from the interface between 2-(4-trifluoromethyl-2-hydroxyphenyl)benzothiazole] zinc and N,N′-diphenyl-N,N′- bis(1-naphthyl)-(1,1′-biphenyl)-4,4′-diamine

The electroplex between (2-(4-trifluoromethyl-2-hydroxyphenyl)benzothiazole) zinc [Zn(4-TfmBTZ)₂] as an electron-acceptor and N,N′-diphenyl-N,N′-bis(1-naphthyl)-(1,1′-biphenyl)-4,4′-diamine (NPB) as an electron-donor was characterized by bilayer, blend, and multilayer quantum-well (MQW) device, respectively. The blend composition and quantum-well number are effective parameters for tuning electroluminescence color. White light with high color purity and color rendering index (CRI) was observed from these devices based on Zn(4-TfmBTZ)₂/NPB. Moreover, the blend and MQW devices all exhibit high operation stability, hence excellent color stability. For the device with 5 mol% NPB in blend layer, its Commission International Del’Eclairage (CIE) coordinate region is x=0.28–0.31, y=0.33–0.35 and CRI is 83.3–91.2 at 5–9 V. For MQW structure device with NPB of 60 nm thickness, its CIE coordinate region is x=0.29–0.32, y=0.31–0.34 and CRI=87.9–92.5 at 10–15 V. Such high color stability and purity and CRI, being close to ideal white light, are of current important for white OLED.     

Measurements of work function of pristine and CuI doped carbon nanotubes

We report the results on measurements of the work function of carbon nanotubes and carbon-nanotube-based materials including pristine multi-walled and single-walled carbon nanotubes as well as single-walled carbon nanotubes intercalated by CuI with the Kelvin probe technique. We found the work function value 4.97–4.98 eV for pristine carbon nanotubes, while carbon nanotubes infilled with CuI demonstrate the work function value decreased by more than 0.1 eV (4.86–4.96 eV).     

Evolution of the zinc compound nanostructures in zinc acetate single-source solution

A series of nanostructured zinc compounds with different nanostructures such as nanobelts, flake-like, flower-like, and twinning crystals was synthesized using zinc acetate (Zn(Ac)₂) as a single-source. The evolution of the zinc compounds from layered basic zinc acetate (LBZA) to bilayered basic zinc acetate (BLBZA) and twinned ZnO nano/microcrystal was studied. The low-angle X-ray diffraction spectra indicate the layered spacing is 1.34 and 2.1 nm for LBZA and BLBZA, respectively. The Fourier transform infrared (FTIR) spectra results confirmed that the bonding force of acetate anion with zinc cations decreases with the phase transformation from Zn(Ac)₂ to BLBZA, and finally to LBZA. The OH⁻ groups gradually replaced the acetate groups coordinated to the matrix zinc cation, and the acetate groups were released completely. Finally, the Zn(OH)₂ and ZnO were formed at high temperature. The conversion process from Zn(Ac)₂ to ZnO with release of acetate anions can be described as Zn(Ac)₂ → BLBZA → LBZA → Zn(OH)₂ → ZnO.     

Electrical, galvanomagnetic, and thermoelectric properties of PbSe in the void sublattice of opal

A study of transport phenomena, namely, electrical resistivity, thermopower, Hall coefficient, and magnetoresistance of p PbSe synthesized in opal voids has been carried out in the 4–300 K range. The parameters of the semiconducting material have been determined at different void filling levels. An anomalous behavior of the hole mobility associated with surface scattering from insulating opal-matrix walls has been observed. Fiz. Tverd. Tela (St. Petersburg) 40, 781–783 (April 1998)     

In Situ Charge Characterization of TiO<Subscript>2</Subscript> and Cu–TiO<Subscript>2</Subscript> Nanoparticles in a Flame Aerosol Reactor

Charge distribution characteristics were investigated for nanoparticles synthesized in a diffusion flame aerosol reactor. The nanoparticles considered were pristine TiO₂ and Cu–TiO₂, with Cu dopant concentrations ranging from 1 to 5 wt% with particle size from 25 to 60 nm. In situ measurements were conducted by integrating a tandem differential mobility analyzer (TDMA) experimental setup with the flame aerosol reactor. A charging model was used to identify the important parameters that govern the two charging mechanisms (diffusion and thermo-ionization) in the flame and their relative importance at different operating parameters. The results indicate that TiO₂ and Cu–TiO₂ nanoparticles carry single as well as double unit charges. The charged fraction depends on particle size as well as on dopant concentration. The charged fraction increased with increasing particle size and decreased with copper dopant concentration. Measured charged fractions were similar for both the polarities at different mobility diameters. Based on the flame operating parameters, the calculations indicate that diffusion charging is dominant in the flame, which is consistent with the experimental results.     

Paradoxical Brownian motion in a microfluidic device: Absolute negative mobility

We report on a paradoxical migration mechanism in a microstructured lab-on-a-chip environment. The phenomenon is based on a subtle interplay between Brownian motion (thermal noise), a periodic and symmetric microstructure, and a biased AC electric field. The resulting non-linear dynamics far from thermal equilibrium gives rise to absolute negative mobility, i.e. a migrational transport, which is – both for negative and positive bias – always opposite to the net acting force, in good agreement between experiment and theory.     

Vibrational spectra and crystal lattice dynamics of hexahydrates of zinc potassium and ammonium sulfates

The IR spectra and polarized Raman spectra of crystals of hexahydrates of zinc potassium and ammonium sulfates have been obtained experimentally at 93 K and at room temperature. The frequencies and modes of normal vibrations of the octahedral complex [Zn(H₂O)₆]²⁺ have been calculated. The assignment of the observed lines of the internal and external vibrations of the crystal cell has been made by calculations and by factor-group analysis. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 2, pp. 162–168, March–April, 2000.     

Structural features and transport processes of superionic conductors based on tin(II) fluoride

The thermal behavior and transport properties of lead(II) tetrafluorostannate(II) have been investigated by impedance spectroscopy,¹⁹F NMR and high hydrostatic pressure techniques. It is shown that these experimental methods are powerful tools to clarify ionic transport processes in the investigated solid electrolytes with predominant fluorine mobility. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

On a method for detection of subsurface objects from ultrabroadband GPR data

An approach is presented, which allows determination of size and shape of subsurface low-contrast objects from their dielectric properties and location of people and things present inside the buildings from the echo ultrabroadband electromagnetic signals. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 94–99, November, 2008.     

Nano-structuring of PTFE surface by plasma treatment,etching, and sputtering with gold

Properties of pristine, plasma modified, and etched (by water and methanol) polytetrafluoroethylene (PTFE) were studied. Gold nanolayers sputtered on this modified PTFE have been also investigated. Contact angle, measured by goniometry, was studied as a function of plasma exposure and post-exposure aging times. Degradation of polymer chains was examined by etching of plasma modified PTFE in water or methanol. The amount of ablated and etched layer was measured by gravimetry. In the next step the pristine, plasma modified, and etched PTFE was sputtered with gold. Changes in surface morphology were observed using atomic force microscopy. Chemical structure of modified polymers was characterized by X-ray photoelectron spectroscopy (XPS). Surface chemistry of the samples was investigated by electrokinetic analysis. Sheet resistance of the gold layers was measured by two-point technique. The contact angle of the plasma modified PTFE decreases with increasing exposure time. The PTFE amount, ablated by the plasma treatment, increases with the plasma exposure time. XPS measurements proved that during the plasma treatment the PTFE macromolecular chains are degraded and oxidized and new –C–O–C–, –C=O, and –O–C=O groups are created in modified surface layer. Surface of the plasma modified PTFE is weakly soluble in methanol and intensively soluble in water. Zeta potential and XPS shown dramatic changes in PTFE surface chemistry after the plasma exposure, water etching, and gold deposition. When continuous gold layer is formed a rapid decrease of the sheet resistance of the gold layer is observed.     

Temperature and electric field dependences of the mobility of electrons in vertical transport in GaAs/Ga<Subscript>1−<Emphasis Type="Italic">y</Emphasis></Subscript>Al<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>As barrier structures containing quantum wells

The mobility of electrons in vertical transport in GaAs/Ga_1−y Al _y As barrier structures was investigated using geometric magnetoresistance measurements in the dark. The samples studied had Ga_1−y Al _y As (0 ≤ y ≤ 0:26) linearly graded barriers between the n⁺-GaAs contacts and the Ga_0:74Al_0:26As central barrier, which contain N _w (=0, 2, 4, 7 and 10) n-doped GaAs quantum wells. The mobility was determined as functions of (i) temperature (80–290 K) at low applied voltage (0.01–0.1 V) and (ii) applied voltage (0.005–1.6 V) at selected temperatures in the range 3.5–290 K. The experimental results for the temperature dependence of low-field mobility suggest that space-charge scattering is dominant in the samples with N _w =0 and 2, whereas ionized impurity scattering is dominant in the samples with N _w =4, 7 and 10. The effect of polar optical phonon scattering on the mobility becomes significant in all barrier structures at temperatures above about 200 K. The difference between the measured mobility and the calculated total mobility in the samples with N _w =4, 7 and 10, observed above 200 K, is attributed to the reflection of electrons from well-barrier interfaces in the quantum wells and interface roughness scattering. The rapid decrease of mobility with applied voltage at high voltages is explained by intervalley scattering of hot electrons.