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At least 613 records · Page 34

Radionuclide uptake by colloidal and particulate humic acids obtained from 14 soils collected worldwide

Uptake of six particle-reactive and/or redox-sensitive radionuclides ( 210 Pb, 234 Th, 7 Be, 59 Fe, 237 Np and 233 Pa) by 14 humic acids (HAs) was investigated in artificial groundwater under mildly acidic conditions (pH~5.5). In HA-groundwater slurry, Pb, Be, Fe and Pa bound strongly to particulate HA (>0.45 μm), supporting their application as tracers of soil erosion. Th bound strongly to the colloidal HA (3 kDa- 0.45 μm) and as such, would not be a good candidate as a tracer for monitoring soil erosion. HAs likely reduced the oxidized neptunyl form (Np(V)O 4 +) to Np(IV) based on its enhanced particle-reactivity and Np uptake by particulate HAs, partially retarding the movement of anthropogenic 237 Np in field polluted environments. Particulate/colloidal carbonyl/O-aryl (likely through hydroquinone/quinone) functionalities in the HA correlated to Np and Pa uptake, but only particulate O-aryl functionalities was responsible for Fe uptake. The carboxylate- and carbonyl/O-aryl-containing organic functionalities in the HA correlated strongly with Th uptake. In contrast, no significant correlations between organic parameters and Pb or Be uptake implied their predominance of uniform surface adsorption onto particles. Our work provides novel insight into the binding of six radionuclides with different organic functionalities of three size fractions, as well as its possible impact on their application in the soiltracing research.

59 BASIC BIOLOGICAL SCIENCES↗

Synthesis, particle shape characterization, magnetic properties and surface modification of superparamagnetic iron oxide nanochains

We report monodisperse, chain-like particles (nanochains) consisted of silica-coated maghemite (γ-Fe2O3) nanoparticle clusters prepared by colloidal chemistry and magnetic field-induced self-assembly of nanoparticle clusters. In order to quantify the shapes of chain-like particles, we have used the measure for shape convexity which is also called solidity. We functionalize the surface of the nanochains with amino (–NH2) and carboxyl groups (–COOH) in order to modify surface charge. These surfaces of nanochains provide better colloidal stability and their potential for practical applications in biomedicine. The enhanced colloidal stability of the surface modified nanochains is confirmed by Zeta potential (ζ-potential) analysis. Magnetic properties of the nanochains show superparamagnetic state at room temperature since the nanochains are composed of tiny nanoparticles as their building blocks. The measured M(H) data at room temperature have been successfully fitted by the Langevin function and magnetic moment μp = 20,526 μB for sphere-like nanoparticle clusters and μp = 20,767 μB for nanochains are determined. The determined magnetic parameters have revealed that the nanochains show a magnetic moment of the nanoparticles higher than the one of individual nanoparticle clusters. These differences can be attributed to the collective magnetic properties of superparamagnetic iron oxide nanoparticles (SPION) assembled in different morphologies (isotropic and anisotropic morphology). © 2018.

60 APPLIED LIFE SCIENCES↗

Enhanced Luminescent Stability through Particle Interactions in Silicon Nanocrystal Aggregates

Close-packed assemblies of ligand-passivated colloidal nanocrystals can exhibit enhanced photoluminescent stability, but the origin of this effect is unclear. Here, we use experiment, simulation, and ab initio computation to examine the influence of interparticle interactions on the photoluminescent stability of silicon nanocrystal aggregates. The time-dependent photoluminescence emitted by structures ranging in size from a single quantum dot to agglomerates of more than a thousand is compared with Monte Carlo simulations of noninteracting ensembles using measured single-particle blinking data as input. In contrast to the behavior typically exhibited by the metal chalcogenides, the measured photoluminescent stability shows an enhancement with respect to the noninteracting scenario with increasing aggregate size. We model this behavior using time-dependent density functional theory calculations of energy transfer between neighboring nanocrystals as a function of nanocrystal size, separation, and the presence of charge and/or surface-passivation defects. In conclusion, our results suggest that rapid exciton transfer from “bright” nanocrystals to surface trap states in nearest-neighbors can efficiently fill such traps and enhance the stability of emission by promoting the radiative recombination of slowly diffusing excited electrons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polishing slurry preventing agglomeration of charged colloids without loss of surface activity

A method for chemically stabilizing polishing slurries in aqueous suspension to prevent their agglomeration while maintaining their surface activity is disclosed. The method prevents the formation of irreversible particle agglomerates during drying and permits the subsequent re-suspension of dried particles with no impact on the particle size distribution. The stabilization method can be customized based on knowledge of the colloid surface charge at suspension pH conditions, addition of a charged species having like charge to the colloid at the suspension conditions, and control of the concentrations of the charged species and other ions in suspension.

Dylia-Spears, Rebecca↗

Structural Emergence in Particle Dispersions

Particle dispersions, such as pigment-based inks, comprise weakly bound, milled nanoparticles. The properties of these pigments depend on both their chemical composition and a rather complex structural hierarchy which emerges from these dispersions. The emergence of structure under semidilute conditions is related to the structure of the dilute particles, the particle spacing (mesh size), processing history, and the interaction potential. Kinetic simulations could predict such emergence using these input parameters. In this paper, organic pigments are studied as an example of the importance of emergent structure to predict properties such as brilliance and opacity. Organic pigments are used to impart color to commercial inks, plastics, coatings, and cosmetics. In many cases, dilute pigments are mass fractal structures consisting of aggregated nanoparticles held together by weak van der Waals forces. In water, surfactant is added to create a pigment dispersion (an ink). The final properties of a pigment emerge from a complex interplay between aggregation and dispersion of aggregates as a function of concentration. Samples of the organic pigment yellow 14, PY14, were milled to four primary particle sizes to study the effect on structural emergence. The interaction between surfactant-stabilized PY14 aggregates in an aqueous medium was quantified by the second virial coefficient, A 2 , which reflects long-range interactions. The degree of aggregation is associated with short-range attractive interactions between primary particles. In this series of pigments, the degree of aggregation increases dramatically with reduction in primary particle size. Concurrently, the second-order virial coefficient, A 2 , increases reflecting stronger long-range repulsive interactions with particle size. Structural emergence can be understood through the percolation concentration and the filler mesh size. A 2 is translated into a repulsive interaction potential for use in dissipative particle dynamics simulations to enable predictive modeling. Furthermore, this description of the interactions between dispersed pigment aggregates allows for a more scientific and predictive approach to understand structural emergence.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Directed assembly of hybrid nanostructures using optically resonant nanotweezers

This represents the final report for this project. Over the course of the project we have made significant progress in photonically driven nano-assembly including: (1) demonstrating the first direct optical tweezer based manipulation of proteins, (2) the ability to apply optical angular torques to microtubuals and other rod-shaped microparticles, (3) direct assembly of hybrid nanostructures comprising of polymeric nanoparticles and carbon nanotubes and, (4) the ability to drive biological reactions (specifically protein aggregation) that are thermodynamically unfavorable by applying localized optical work. These advancements are described in the list of papers provided in section 2.0 of the below. Summary details are provided in prior year annual reports. We have two additional papers which will be submitted shortly based on the work done under this award. An updated publication list will be provided to the program manager when those are accepted. In this report, we report on a new advancement made in the final project year, which uses the nanotweezer technology to perform direct measurements of particle-surface interactions. Briefly, these measurements are important for characterizing the stability and behavior of colloidal and nanoparticle suspensions and current techniques are limited in their ability to measure piconewton scale interaction forces on sub-micrometer particles due to signal detection limits and thermal noise. In this project year we developed a new technique called “Nanophotonic Force Microscopy” which uses the localized region of exponentially decaying, near-field, light to confine small particles close to a surface. From the statistical distribution of the light intensity scattered by the particle the technique maps out the potential well of the trap and directly quantify the repulsive force between the nanoparticle and the surface. The major advantage of the technique is that it can measure forces and energy wells below the thermal noise limit, resolving interaction forces smaller than 1 pN on dielectric particles as small as 100 nm in diameter.

36 MATERIALS SCIENCE↗

Electric-field–induced assembly and propulsion of chiral colloidal clusters

Chiral molecules with opposite handedness exhibit distinct physical, chemical, or biological properties. They pose challenges as well as opportunities in understanding the phase behavior of soft matter, designing enantioselective catalysts, and manufacturing single-handed pharmaceuticals. Microscopic particles, arranged in a chiral configuration, could also exhibit unusual optical, electric, or magnetic responses. In this paper, we report a simple method to assemble achiral building blocks, i.e., the asymmetric colloidal dimers, into a family of chiral clusters. Under alternating current electric fields, two to four lying dimers associate closely with a central standing dimer and form both right- and left-handed clusters on a conducting substrate. The cluster configuration is primarily determined by the induced dipolar interactions between constituent dimers. Our theoretical model reveals that in-plane dipolar repulsion between petals in the cluster favors the achiral configuration, whereas out-of-plane attraction between the central dimer and surrounding petals favors a chiral arrangement. It is the competition between these two interactions that dictates the final configuration. The theoretical chirality phase diagram is found to be in excellent agreement with experimental observations. We further demonstrate that the broken symmetry in chiral clusters induces an unbalanced electrohydrodynamic flow surrounding them. As a result, they rotate in opposite directions according to their handedness. Both the assembly and propulsion mechanisms revealed here can be potentially applied to other types of asymmetric particles. Lastly, such kinds of chiral colloids will be useful for fabricating metamaterials, making model systems for both chiral molecules and active matter, or building propellers for microscale transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanopore networks in colloidal silica assemblies characterized by XCT for confined fluid flow modeling

Fluid flow through nanopore structures has exhibited different behavior than that described by Darcy's law, derived from pore networks of micrometer scale. Here, pressure assemblies of colloidal silica spheres of specified diameters from 94 to 620 nanometers were prepared as model nano-porous media. The smaller silica spheres tended to form random packing, but some substantial ordering was found in the packing of the larger silica spheres. X-ray computed tomography (XCT), with a voxel resolution of 16 nm, was used to characterize the nanopore networks. The porosity of the Nano-XCT pore network (34%) was less than the total porosity of the assemblies as determined by X-ray attenuation (52%), possibly due to the limits of voxel resolution during segmentation. Fluid flow in the nanopore networks was simulated using the single-phase Lattice Boltzmann Method, and the simulated permeability was compared with the empirical and experimental values. Based on our characterization, although a well-ordered packing of silica spheres was not achieved, it was found that the nanopore networks in the colloidal silica assemblies had pore size distributions corresponding to the particle sizes. The simulated permeability was less than the experimental measurement for water flow, but the complex packing of silica spheres and surface chemistry issues need to be considered in future research.

02 PETROLEUM↗

Size controlled near-infrared high-quality PbSe quantum dots

Herein, we report the size controlled preparation of PbSe quantum dots (QDs) by non coordinating solvent route using oleic acid as surfactant molecules. The particles size is controlled by varying temperature and time of reaction. The present method of synthesis gives highly stable colloids, spherical in shape, better size tunability, narrow size distribution, extremely small size, monodisperse and exhibit strong near-infrared emission. The estimated particles sizes are in the range of 2 to 8 nm. These PbSe quantum dots are used for applications in optoelectronics and biological imaging.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Fabrication and characterization of multifunctional Fe/TiO2 composite coatings

Highlights: • Electrodeposition of Fe/TiO{sub 2} composite coatings using methanesulfonate electrolytes. • TiO{sub 2} sol is synthesized by means of precipitation technique. • Electrodeposition kinetics obeys the improved Guglielmi's model. • Incorporation of TiO{sub 2} into Fe matrix results in an increase in microhardness. • Enhanced electrocatalytic and photocatalytic activity of Fe/TiO{sub 2} composites. - Abstract: Composite Fe/TiO{sub 2} coatings were electrodeposited using environmentally friendly colloidal methanesulfonate electrolytes. A sol of titania nano-particles was synthesized by means of precipitation technique. The electrodeposition parameters and the properties of composite coatings were compared with those typical of analogous composite electrodeposits produced from the plating bath containing suspended commercially available nano-powder Degussa P25. The electrodeposition process obeys the modified Guglielmi's model. The incorporation of TiO{sub 2} dispersed phase into iron matrix results in an appreciable increase in the microhardness due to dispersion strengthening. The microhardness of deposits obtained from electrolyte with the addition of nano-sized titania sol exceeds that which is observed for coatings produced from the bath containing aggregated Degussa P25 TiO{sub 2} particles. The introduction of dioxide titanium particles into Fe matrix yields photocatalytic properties towards the reaction of organic dye degradation and improves electrocatalytic performance towards hydrogen and oxygen evolution reactions.

36 MATERIALS SCIENCE↗

Dopant Mediated Assembly of Cu 2 ZnSnS 4 Nanorods into Atomically Coupled 2D Sheets in Solution

Assembly of anisotropic nanocrystals into ordered superstructures is an area of intense research interest due to its relevance to bring nanocrystal properties to macroscopic length scales and to impart additional collective properties owing to the superstructure. Numerous routes have been explored to assemble such nanocrystal superstructures ranging from self-directed to external field-directed methods. Most of the approaches require sensitive control of experimental parameters that are largely environmental and require extra processing steps, increasing complexity and limiting reproducibility. Here, we demonstrate a simple approach to assemble colloidal nanorods in situ, wherein dopant incorporation during the particle synthesis results in the formation of preassembled 2D sheets of close-packed ordered arrays of vertically oriented nanorods in solution.

36 MATERIALS SCIENCE↗

Femtosecond laser generated gold nanoparticles and their plasmonic properties

The pulsed laser ablation in liquid medium is now commonly used to generate stable colloidal nanoparticles (NPs) in absence of any chemical additives or stabilizer with diverse applications. In this paper, we report generation of gold NPs (Au NPs) by ultra-short laser pulses. Femtosecond (fs) laser radiation (λ = 800 nm) has been used to ablate a gold target in pure de-ionized water to produce gold colloids with smallsize distribution. The average size of the particles can be further controlled by subjecting to laser-induced post-irradiation providing a versatile physical method of size-selected gold nanoparticles. The optical extinction and morphological dimensions were investigated with UV-Vis spectroscopy and Transmission Electron Microscopy measurements, respectively. Finite difference time domain (FDTD) method is employed to calculate localized surface plasmon (LSPR) wavelength and the near-field generated by Au NPs and their hybrids.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Understanding the creation of & reducing surface microroughness during polishing & post-processing of glass optics

In the follow study, we have developed a detailed understanding of the chemical and mechanical microscopic interactions that occur during polishing affecting the resulting surface microroughness of the workpiece. Through targeted experiments and modeling, the quantitative relationships of many important polishing parameters & characteristics affecting surface microroughness have been determined. These behaviors and phenomena have been described by a number of models including: (a) the Ensemble Hertzian Multi Gap (EHMG) model used to predict the removal rate and roughness at atomic force microscope (AFM) scale lengths as a function of various polishing parameters, (b) the Island Distribution Gap (IDG) model used to predict the roughness at larger scale lengths, (c) the Deraguin-Verwey-Landau-Overbeek (DLVO) 3-body electrostatic colloidal model used to predict the interaction of slurry particles at the interface and roughness behavior as a function of pH, and (d) a diffusion/chemical reaction rate model of the incorporation of impurities species into the polishing surface layer (called the Bielby layer). Based on this improved understanding, novel strategies to polish the workpiece have been developed simultaneously leading to both ultrasmooth surfaces and high material removal rates. Some of these strategies include: (a) use of narrow PSD slurries, (b) a novel diamond conditioning recipe of the lap to increase the active contact area between the workpiece and lap without destroying its surface figure, (c) proper control of pH for a given glass type to allow for a uniform distribution of slurry particles at the interface, and (d) increase in applied load just up to the transition between molecular to plastic removal regime for a single slurry particle. These techniques have been incorporated into a previously developed finishing process called Convergent Polishing leading to not just economical finishing process with improved surface figure control, but also simultaneously leading to low roughness surface with high removal rates.

36 MATERIALS SCIENCE↗

Processing of laser formed SiC powder

Superior SiC characteristics can be achieved through the use of ideal constituent powders and careful post-synthesis processing steps. High purity SiC powders of approx. 1000 A uniform diameter, nonagglomerated and spherical were produced. This required major revision of the particle formation and growth model from one based on classical nucleation and growth to one based on collision and coalescence of Si particles followed by their carburization. Dispersions based on pure organic solvents as well as steric stabilization were investigated. Although stable dispersions were formed by both, subsequent part fabrication emphasized the pure solvents since fewer problems with drying and residuals of the high purity particles were anticipated. Test parts were made by the colloidal pressing technique; both liquid filtration and consolidation (rearrangement) stages were modeled. Green densities corresponding to a random close packed structure (approx. 63%) were achieved; this highly perfect structure has a high, uniform coordination number (greater than 11) approaching the quality of an ordered structure without introducing domain boundary effects. After drying, parts were densified at temperatures ranging from 1800 to 2100 C. Optimum densification temperatures will probably be in the 1900 to 2000 C range based on these preliminary results which showed that 2050 C samples had experienced substantial grain growth. Although overfired, the 2050 C samples exhibited excellent mechanical properties. Biaxial tensile strengths up to 714 MPa and Vickers hardness values of 2430 kg/sq mm 2 were both more typical of hot pressed than sintered SiC. Both result from the absence of large defects and the confinement of residual porosity (less than 2.5%) to small diameter, uniformly distributed pores.

Haggerty, J. S.↗

Occurrence and Stabilization of Colloidal and Nanoparticulate Mercury Sulfides (Final Technical Report)

Mercury contaminates the soils at several DOE sites, including facilities at Oak Ridge, Hanford, and the Savannah River site. This contamination poses a hazard to surrounding ecosystems because the metal continuously leaches to local streams and rivers and is converted to methylmercury, a neurotoxic and highly bioaccumulative form of mercury. Anaerobic microorganisms such as sulfate-reducing and iron-reducing bacteria are primarily responsible for methylmercury production in the environment. The remediation of mercury-contaminated ecosystems is difficult because we lack a poor understanding of the factors that control mercury mobilization and methylation in sediments. The objective of this project was to investigate the forms of mercury that are bioavailable to methylating bacteria. This project specifically focused on mercury-sulfide-organic matter geochemistry and the persistence of nanoparticulate HgS that are intermediates of metal sulfide precipitation reactions occurring in the presence of natural organic matter (NOM). This work involved two specific aims: 1) Investigate environmental processes that facilitate the occurrence and stabilization of nanoparticulate HgS and other metal sulfides; and (2) Investigate the occurrence of nanoparticulate HgS in sediments of the East Fork Poplar Creek, located in near a DOE facility in Oak Ridge, TN. For specific aim #1, laboratory experiments were performed to simulate metal sulfide precipitation processes in environmental systems. A key experimental variable was the type and concentration of NOM that was used in the experiments simulating metal sulfide precipitation. The characteristics of the metal sulfide nanoparticles were analyzed using a suite of analytical techniques that included X-ray based methods at DOE synchrotron facilities (National Synchrotron Light Source and Advanced Photon Source). Field sampling in Oak Ridge was performed in collaboration with colleague at the Oak Ridge National Laboratory. The experimental results demonstrated that a combination of photon scattering and spectroscopic tools can be used to characterize nanoscale structures that form during heterogeneous metal-sulfide-NOM precipitation. ZnS precipitation experiments with a low molecular weight thiol indicated the importance of specific metal-ligand binding for altering the kinetics of ZnS nanoparticle aggregation and monomer growth. However, NOM consists of macromolecular structures that may interact with nano-HgS in non-specific ways (e.g. electrosteric surface interactions. The methylation potential of nano-HgS in sediments may depend on size and crystallinity of nanoparticles and interactions with NOM. For specific aim #2, sediment core samples were collected in three separate locations along the East Fork Poplar Creek in Oak Ridge, TN in June 2011. Analysis of the sediment samples indicated that more than 90% of the Hg in the porewater is associated with colloidal material. These results highlight the importance of small particles for dominating Hg speciation in sediment porewater. Overall, this project highlights the importance of nanoscale phases for mercury speciation. Nanoparticulate HgS will be of particular importance in the anaerobic habitats of methylating microorganisms. In previous models for Hg bioavailability, nanoparticles of Hg are presumed to be unavailable for methylating bacteria. However, recent work shows that nanoparticles contribute to bioavailable Hg that greatly exceeds the contribution from larger HgS microparticles (Zhang et al., 2012). The work performed for this exploratory project lays the groundwork for further study on nanoscale mercury sulfide geochemistry and contributes to an improved understanding of Hg bioavailability and methylation potential.

54 ENVIRONMENTAL SCIENCES↗

Bright and durable scintillation from colloidal quantum shells

Abstract Efficient, fast, and robust scintillators for ionizing radiation detection are crucial in various fields, including medical diagnostics, defense, and particle physics. However, traditional scintillator technologies face challenges in simultaneously achieving optimal performance and high-speed operation. Herein we introduce colloidal quantum shell heterostructures as X-ray and electron scintillators, combining efficiency, speed, and durability. Quantum shells exhibit light yields up to 70,000 photons MeV −1 at room temperature, enabled by their high multiexciton radiative efficiency thanks to long Auger-Meitner lifetimes (>10 ns). Radioluminescence is fast, with lifetimes of 2.5 ns and sub-100 ps rise times. Additionally, quantum shells do not exhibit afterglow and maintain stable scintillation even under high X-ray doses (>10 9 Gy). Furthermore, we showcase quantum shells for X-ray imaging achieving a spatial resolution as high as 28 line pairs per millimeter. Overall, efficient, fast, and durable scintillation make quantum shells appealing in applications ranging from ultrafast radiation detection to high-resolution imaging.

47 OTHER INSTRUMENTATION↗

SINGLE: Atomic-resolution structure identification of nanocrystals by graphene liquid cell EM

Analysis of the three-dimensional (3D) structures of nanocrystals with solution-phase transmission electron microscopy is beginning to reveal their unique physiochemical properties. We developed a “one-particle Brownian 3D reconstruction method” based on imaging of ensembles of colloidal nanocrystals using graphene liquid cell electron microscopy. Projection images of differently rotated nanocrystals are acquired using a direct electron detector with high temporal (<2.5 ms) resolution and analyzed to obtain an ensemble of 3D reconstructions. Here, we introduce computational methods required for successful atomic-resolution 3D reconstruction: (i) tracking of the individual particles throughout the time series, (ii) subtraction of the interfering background of the graphene liquid cell, (iii) identification and rejection of low-quality images, and (iv) tailored strategies for 2D/3D alignment and averaging that differ from those used in biological cryo–electron microscopy. Our developments are made available through the open-source software package SINGLE.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗