Search NASA⌕ Search

SEARCH · Search NASA

Results for “Colloidal particles”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 847 records · Page 47

Entropic depletion in colloidal suspensions and polymer liquids: Role of nanoparticle surface topography

Here, we employ a hybrid Monte Carlo plus integral equation theory approach to study how dense fluids of small nanoparticles or polymer chains mediate entropic depletion interactions between topographically rough particles where all interaction potentials are hard core repulsion. The corrugated particle surfaces are composed of densely packed beads which present variable degrees of controlled topographic roughness and free volume associated with their geometric crevices. This pure entropy problem is characterized by competing ideal translational and (favorable and unfavorable) excess entropic contributions. Surface roughness generically reduces particle depletion aggregation relative to the smooth hard sphere case. However, the competition between ideal and excess packing entropy effects in the bulk, near the particle surface and in the crevices, results in a non-monotonic variation of the particle-monomer packing correlation function as a function of the two dimensionless length scale ratios that quantify the effective surface roughness. As a result, the inter-particle potential of mean force (PMF), second virial coefficient, and spinodal miscibility volume fraction vary non-monotonically with the surface bead to monomer diameter and particle core to surface bead diameter ratios. A miscibility window is predicted corresponding to an optimum degree of surface roughness that completely destroys depletion attraction resulting in a repulsive PMF. Variation of the (dense) matrix packing fraction can enhance or suppress particle miscibility depending upon the amount of surface roughness. Connecting the monomers into polymer chains destabilizes the system via enhanced contact depletion attraction, but the non-monotonic variations with surface roughness metrics persist.

36 MATERIALS SCIENCE↗

New Programs Utilizing Light Scattering and Flow Imaging Techniques for Macromolecular Crystal Growth and Fluid Dynamics Studies

Dr. Phil Segre, a physicist by training, is a recent addition to the Biotech group, SD46, having joined NASA in August of 2000. Over the past two years he has been developing a laboratory for the study of macromolecular and protein crystal growth. The main apparatus for this work is a Dynamic Light Scattering apparatus, DLS, which is capable of making highly precise measurements of size distributions of both protein solutions and protein crystals. With Drs. Chernov and Thomas (USRA), he has begun a collaboration studying the affects of protein impurities on protein crystal growth and subsequent crystal quality. One of the hypotheses behind the differences between Earth and space grown protein crystals is that the absorption of harmful impurities is reduced in space due to the absence of convective flows. Using DLS measurements we are examining crystal growth with varying amounts of impurities and testing whether there is a strong physical basis behind this hypothesis. With Dr. Joe Ng of UAH he has been collaborating on a project to examine the folding/unfolding dynamics of large RNA complexes. A detailed understanding of this process is necessary for the handling of RNA in biotech applications, and the DLS instrument gives details and results beyond that of other instruments. With Prof. Jim McClymer of the University of Maine (summer faculty visitor to NASA in 2001, 2002), we have been studying the crystallization process in model colloidal suspensions whose behavior in some cases can mimic that of much smaller protein solutions. An understanding of the self-assembly of colloids is the first step in the process of engineering novel materials for photonic and light switching applications. Finally, he has begun an investigation into the physics of particle sedimentation. In addition to the DLS instrument he also has an instrument (called PIV) that can measure flow fields of fluids. The applications are to the dynamics of protein crystal motions both on earth and in low-gravity.

Source record↗

Polar state reversal in active fluids

Spontaneous emergence of correlated states such as flocks and vortices is a prime example of collective dynamics and self-organization observed in active matter. In geometrically confined systems, the formation of globally correlated polar states proceeds through the emergence of a macroscopic steadily rotating vortex, which spontaneously selects a clockwise or counterclockwise global chiral state. In this work, we reveal that a global vortex formed by colloidal rollers exhibits polar state reversal and that a subsequent formation of the collective states upon re-energizing the system is not random. We combine experiments and simulations to elucidate how a combination of hydrodynamic and electrostatic interactions leads to hidden asymmetries in the local particle positional order, reflecting the chiral state of the system. These asymmetries can be exploited to systematically command subsequent polar states of active liquids through temporal control of the activity.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Molecular structures of dissolved and colloidal As V –Fe III complexes and their roles in the mobilization of As V under strongly acidic conditions

The effect of high concentration of iron (Fe III ) on the speciation and mobility of arsenic (As) under strongly acidic conditions remains unclear. This work studied the redistribution and speciation of As V and Fe III at Fe/As molar ratio of 1–14 and pH 1.5–2.0 in the dissolved, colloidal, and solid phases. Results showed that the elevated Fe III induced the decomposition of the precipitated poorly crystalline ferric arsenate by forming dissolved (< 3 kDa) and colloidal (3 kDa–0.1 µm) As–Fe complexes. The fraction of particulate As (> 0.1 µm) decreased from 70–90% to less than 20% when the Fe/As molar ratio increased from 1 to 14. The particle size of the bulk samples decreased significantly with the increase of Fe III concentration. The FTIR results suggested that AsV in dissolved/colloidal As–Fe complexes dominantly occurred as HAsO 4 2– species. The EXAFS results indicated that each HAsO 4 2– coordinated with approximately two Fe atoms in dissolved/colloidal As–Fe complexes at Fe/As ≥ 2. Furthermore, the findings suggest that high aqueous Fe III concentration can promote the mobility of As by forming dissolved/colloidal Fe–As complexes in acidic waters, potentially accelerating As transport from source to downstream in acid mine drainage systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Specific features of ZnCdS nanoparticles synthesized in different solvents

Stable colloidal solutions of ZnCdS nanoparticles (3–6 nm in diameter) in polyvinyl alcohol, polyethylene glycol, and H{sub 2}O are produced. The size of the synthesized nanoparticles is independent of the relation between precursors. It is shown that stabilization of the particles is defined by the charge-stability factor and can be attained without any additional stabilizing additives. The ZnCdS quantum dots synthesized emit in a wide spectral range from 450 to 600 nm.

36 MATERIALS SCIENCE↗

Infrared Imaging Using Thermally Stable HgTe/CdS Nanocrystals

Transferring nanocrystals (NCs) from the laboratory environment toward practical applications has raised new challenges. HgTe appears as the most spectrally tunable infrared colloidal platform. Its low-temperature synthesis reduces the growth energy cost yet also favors sintering. Once coupled to a read-out circuit, the Joule effect aggregates the particles, leading to a poorly defined optical edge and large dark current. Here, in this study, we demonstrate that CdS shells bring the expected thermal stability (no redshift upon annealing, reduced tendency to form amalgams, and preservation of photoconduction after an atomic layer deposition process). The electronic structure of these confined particles is unveiled using k.p self-consistent simulations showing a significant exciton binding energy of ~ 200 meV. After shelling, the material displays a p-type behavior that favors the generation of photoconductive gain. The latter is then used to increase the external quantum efficiency of an infrared imager, which now reaches 40% while presenting long-term stability.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Fluid Physics in a Fluctuating Acceleration Environment

Our program of research aims at developing a stochastic description of the residual acceleration field onboard spacecraft (g-jitter) to describe in quantitative detail its effect on fluid motion. Our main premise is that such a statistical description is necessary in those cases in which the characteristic time scales of the process under investigation are long compared with the correlation time of g-jitter. Although a clear separation between time scales makes this approach feasible, there remain several difficulties of practical nature: (i), g-jitter time series are not statistically stationary but rather show definite dependences on factors such as active or rest crew periods; (ii), it is very difficult to extract reliably the low frequency range of the power spectrum of the acceleration field. This range controls the magnitude of diffusive processes; and (iii), models used to date are Gaussian, but there is evidence that large amplitude disturbances occur much more frequently than a Gaussian distribution would predict. The lack of stationarity does not constitute a severe limitation in practice, since the intensity of the stochastic components changes very slowly during space missions (perhaps over times of the order of hours). A separate analysis of large amplitude disturbances has not been undertaken yet, but it does not seem difficult a priori to devise models that may describe this range better than a Gaussian distribution. The effect of low frequency components, on the other hand, is more difficult to ascertain, partly due to the difficulty associated with measuring them, and partly because they may be indistinguishable from slowly changing averages. This latter effect is further complicated by the lack of statistical stationarity of the time series. Recent work has focused on the effect of stochastic modulation on the onset of oscillatory instabilities as an example of resonant interaction between the driving acceleration and normal modes of the system, and on cavity flow as an example of how an oscillatory response under periodic driving becomes diffusive if the forcing is random instead. This paper describes three different topics that illustrate behavior that is peculiar to a stochastic acceleration field. In the first case, we show that g-jitter can induce effective attractive or repulsive forces between a pair of spherical particles that are suspended in an incompressible fluid of different density provided that the momentum diffusion length is larger than the interparticle separation (as in the case in most colloidal suspensions). Second, a stochastic modulation of the control parameter in the vicinity of a pitchfork or supercritical bifurcation is known not to affect the location of the threshold. We show, however, that resonance between the modulation and linearly stable modes close to onset can lead to a shift in threshold. Finally, we discuss the classical problem of vorticity diffusion away from a plane boundary that is being vibrated along its own plane. Periodic motion with zero average vorticity production results in an exponential decay of the vorticity away from the boundary. Random vibration, on the other hand, results in power law decay away from the boundary even if vorticity production averages to zero.

Drolet, Francois↗

Thermal Characterization of Fe3O4 Nanoparticles Formed from Poorly Crystalline Siderite

Increasing interest in environmental geochemistry has led to the recognition that crystals with sizes in the nanometer range (e.g., colloids and nanoscale precipitates) and poorly crystalline compounds (e.g., ferrihydrites) may comprise the majority of reactive mineral surface area near the Earth s surface. When the diameters of individual particles are in the range of 100 nm or less, the surface energy contribution to the free energy modifies phase stability. This results in stabilization of polymorphs not normally encountered in the macrocrystal domain. These phases potentially have very different surface-site geometries, adsorptive properties, and growth mechanisms, and exhibit size-dependent kinetic behavior. Thus nanophases dramatically modify the physical and chemical properties of soils and sediments. In a more general sense, the characteristics of nanocrystals are of intense technological interest because small particle size confers novel chemical, optical, and electronic properties. Thus, nanocrystalline materials are finding applications as catalytic substrates, gas phase separation materials, and even more importantly in the field of medicine. This is an opportune time for mineral physicists working on nanocrystalline materials to develop collaborative efforts with materials scientists, chemists, and others working on nanophase materials of technological interest (e.g., for magnetic memories). Our objective in this study was to synthesize submicron (<200 nm) magnetite and to study their thermal and particle size properties.

Lauer, H. V., Jr.↗

Binary Colloidal Alloy Test-5: Aspheres

The Binary Colloidal Alloy Test - 5: Aspheres (BCAT-5-Aspheres) experiment photographs initially randomized colloidal samples (tiny nanoscale spheres suspended in liquid) in microgravity to determine their resulting structure over time. BCAT-5-Aspheres will study the properties of concentrated systems of small particles when they are identical, but not spherical in microgravity..

Chaikin, Paul M.↗

Nanoplastic removal function and the mechanical nature of colloidal silica slurry polishing

The nanomechanical deformations on a broad range of optical material surfaces (single crystals of Al 2 O 3 [sapphire], SiC, Y 3 Al 5 O 12 [YAG], CaF 2 , and LiB 3 O 5 [LBO]; a SiO 2 –Al 2 O 3 –P 2 O 5 –Li 2 O glass-ceramics [Zerodur]; and glasses of SiO 2 :TiO 2 [ULE], SiO 2 [fused silica], and P 2 O 5 –Al 2 O 3 –K 2 O–BaO [Phosphate]) near the elastic-plastic load boundary have been measured by nanoindentation and nanoscratching to mimic the nanoplastic removal caused by a single slurry particle during polishing. Nanoindenation in air was performed to determine the workpiece hardness at various loads using a commercial nanoindenter with a Berkovich tip. Similarly, an atomic force microscope (AFM) with a stiff diamond coated tip (150 nm radius) was used to produce nanoplastic scratches in air and aqueous environments over a range of applied loads (~20-170 μN). The resulting nanoplastic deformation of the nanoscratches were used to calculate the removal function (i.e., depth per pass) which ranged from 0.18 to 3.6 nm per pass for these materials. A linear correlation between the nanoplastic removal function and the polishing rate (using a fixed polishing process with colloidal silica slurry on a polyurethane pad) of these materials was observed implying that: (a) the polishing mechanism using colloidal silica slurry can be dominated by mechanical rather than chemical interactions; and (b) the nanoplastic removal function, as opposed to interface particle interactions, is the controlling factor for the polishing material removal rate. Furthermore, this correlation is consistent with the Ensemble Hertzian Multi-Gap (EHMG) microscopic material removal rate model described previously. The nanoplastic removal depth was also found to correlate to the measured nanoindentation hardness (H1) of the optical material, scaling as H 1 -3.5 . Two-dimensional (2D) finite element analysis simulations of nanoindentation showed a similar nonlinear dependence of plastic deformation with the workpiece material hardness. The findings of this study are used to determine an effective Preston coefficient for the material removal rate expression and enhance the predictive nature of the nanoplastic polishing rate for various materials utilizing their material properties.

36 MATERIALS SCIENCE↗

Large-scale Manufacturing of Nanoparticulate-based Lubrication Additives for Improved Energy Efficiency and Reduced Emissions

This project was funded under the Department of Energy (DOE) Lab Call on Nanomanufacturing for Energy Efficiency and was directed toward the development of novel boron-based nanocolloidal lubrication additives for improving the friction and wear performance of machine components in a wide range of industrial and transportation applications. Argonne's research team concentrated on the scientific and technical aspects of the project, using a range of state-of-the art analytical and tribological test facilities. Argonne has extensive past experience and expertise in working with boron-based solid and liquid lubrication additives, and has intellectual property ownership of several. There were two industrial collaborators in this project: Ashland Oil (represented by its Valvoline subsidiary) and Primet Precision Materials, Inc. (a leading nanomaterials company). There was also a sub-contract with the University of Arkansas. The major objectives of the project were to develop novel boron-based nanocolloidal lubrication additives and to optimize and verify their performance under boundary-lubricated sliding conditions. The project also tackled problems related to colloidal dispersion, larger-scale manufacturing and blending of nano-additives with base carrier oils. Other important issues dealt with in the project were determination of the optimum size and concentration of the particles and compatibility with various base fluids and/or additives. Boron-based particulate additives considered in this project included boric acid (H 3 BO 3 ), hexagonal boron nitride (h-BN), boron oxide, and borax. As part of this project, we also explored a hybrid MoS 2 + boric acid formulation approach for more effective lubrication and reported the results. The major motivation behind this work was to reduce energy losses related to friction and wear in a wide spectrum of mechanical systems and thereby reduce our dependence on imported oil. Growing concern over greenhouse gas emissions was also a major reason. The transportation sector alone consumes about 13 million barrels of crude oil per day (nearly 60% of which is imported) and is responsible for about 30% of the CO 2 emission. When we consider manufacturing and other energy-intensive industrial processes, the amount of petroleum being consumed due to friction and wear reaches more than 20 million barrels per day (from official energy statistics, U.S. Energy Information Administration). Frequent remanufacturing and/or replacement of worn parts due to friction-, wear-, and scuffing-related degradations also consume significant amounts of energy and give rise to additional CO 2 emission. Overall, the total annual cost of friction- and wear-related energy and material losses is estimated to be rather significant (i.e., as much as 5% of the gross national products of highly industrialized nations). It is projected that more than half of the total friction- and wear-related energy losses can be recovered by developing and implementing advanced friction and wear control technologies. In transportation vehicles alone, 10% to 15% of the fuel energy is spent to overcome friction. If we can cut down the friction- and wear-related energy losses by half, then we can potentially save up to 1.5 million barrels of petroleum per day. Also, less friction and wear would mean less energy consumption as well as less carbon emissions and hazardous byproducts being generated and released to the environment. New and more robust anti-friction and -wear control technologies may thus have a significant positive impact on improving the efficiency and environmental cleanliness of the current legacy fleet and future transportation systems. Effective control of friction in other industrial sectors such as manufacturing, power generation, mining and oil exploration, and agricultural and earthmoving machinery may bring more energy savings. Therefore, this project was timely and responsive to the energy and environmental objectives of DOE and our nation. In this project, most of the boron-based materials with known and potential anti-friction and -wear properties have been manufactured as colloidal additives and tested for their effectiveness in controlling friction and wear. Unlike other anti-friction and -wear additives, which consist of zinc, molybdenum, sulfur, phosphorus, and even chlorine, lubricious boron compounds considered in this project are made of boron, oxygen, nitrogen, and hydrogen, which are more environmentally benign. Among others, boric acid is a natural mineral (known in mineralogy as "sassolite"). Based on our earlier exploratory research, it was found to offer the best overall prospect in terms of performance improvements, environmental friendliness, and ease of manufacturing and, hence, cost effectiveness. Hexagonal boron nitride and borax also offered good prospects for improving the tribological properties of lubricated sliding surfaces. Boron oxide particles were found to be rather hard and somewhat abrasive and, hence, were not considered beyond the initial screening studies. In our bench-top tribological evaluation, we also demonstrated that those additives which worked well with engine oils could work equally well with very common gear oils. When added at appropriate concentrations, such gear oils were found to provide significant resistance to micropitting and scuffing failures in bench-top tribological test systems. Their traction coefficients were also reduced substantially and their scuffing limits were improved considerably. Such impressive tribological behavior of boron-based additives may have been due to their high chemical affinities to interact with sliding contact surfaces and to form slick and protective boundary films. Indeed, our surface studies have confirmed that most of the boron-based nanoparticulate additives prepared in our project possess a strong tendency to form a boron-rich boundary film on sliding contact surfaces. It is believed that the formation of such slick and highly durable boundary films is perhaps one of the fundamental reasons for their superior anti-friction, -wear, and -scuffing performance. Boron-based additives developed under this project have shown potential to reduce or replace the uses of environmentally unsafe sulfur- and phosphorus-bearing anti-wear and friction additives, such as zinc dialkyl dithiophosphate (ZDDP) and molybdenum dialkyl dithiocarbamate (MoDTC), in current lubricating oils. Because ZDDP and MoDTC were suspected of adversely impacting the performance of after-treatment catalysts in current engines, the Environmental Protection Agency (EPA) and other regulatory agencies are demanding that the concentrations of these catalysts in current oils be curtailed drastically. The boron-based nano-additives developed in this project may help reduce the use of ZDDP and MoDTC additives and, hence, help ease the poisoning effects on after-treatment catalysts. When used as lubricity additives, these boron additives can chemically interact with sliding or contacting surfaces and form a protective and slick boundary film, which can, in turn, help reduce friction and wear and increase resistance to scuffing. In the cases of traditional anti-friction and -wear additives mentioned, such protective boundary films result from phosphorus, sulfur, and other elements in the additive package, and again they have been under increased scrutiny in recent years, mainly because of their adverse effects on after-treatment devices. Overall, the boron-based nano-additive technology of this project was shown to hold promise for a broad range of industrial and transportation applications where lower friction and higher resistance to wear and scuffing are needed. Due to more stringent operating conditions of modern machinery, rolling, rotating, and sliding components have been failing to meet the projected lifetimes, mainly because of failures related to mechanical wear, corrosion, and scuffing. The novel boron-based additive technology developed under this project may help such machine components to function reliably by cutting down the friction and wear losses and by increasing resistance to scuffing.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Transport of Explosive Residue Surrogates in Saturated Porous Media

Department of Defense operational ranges may become contaminated by particles of explosives residues (ER) as a result of low-order detonations of munitions. The goal of this study was to determine the extent to which particles of ER could migrate through columns of sandy sediment, representing model aquifer materials. Transport experiments were conducted in saturated columns (2×20 cm) packed with different grain sizes of clean sand or glass beads. Fine particles (approximately 2 to 50 μm) of 2,6- dinitrotoluene (DNT) were used as a surrogate for ER. DNT particles were applied to the top 1 cm of sand or beads in the columns, and the columns were subsequently leached with artificial groundwater solutions. DNT migration occurred as both dissolved and particulate phases. Concentration differences between unfiltered and filtered samples indicate that particulate DNT accounted for up to 41% of the mass recovered in effluent samples. Proportionally, more particulate than dissolved DNT was recovered in effluent solutions from columns with larger grain sizes, while total concentrations of DNT in effluent were inversely related to grain size. Of the total DNT mass applied to the uppermost layer of the column, <3% was recovered in the effluent with the bulk remaining in the top 2 cm of the column. Our results suggest there is some potential for subsurface migration of ER particles and that most of the particles will be retained over relatively short transport distances.

54 ENVIRONMENTAL SCIENCES↗

Colloidal phenomena reflect the interplay between interfacial solution structure, interparticle forces, and dynamical response

The physical and chemical properties of colloidal systems are central to both natural and synthetic processes that enable a wide range of energy and environmental applications. These properties are an emergent outcome of the structure that colloidal systems adopt in response to the interplay of electrical, van der Waals, hydration, and steric forces coupled to the inherent fluctuations of the system. Here, in this study, we review the nature of those forces and show how variations in their relative importance lead to distinct free energy landscapes and consequent dynamic behaviors, illustrated for colloidal dispersions, nanocrystal superlattices, and mesocrystlline solids formed through oriented attachment. We end by discussing the challenges to future progress arising from the need to seamless couple from molecular to particle to ensemble scales.

42 ENGINEERING↗

Engineering Two-Phase and Three-Phase Microstructures from Water-Based Dispersions of Nanoparticles for Eco-Friendly Polymer Solar Cell Applications

Nanoparticle organic photovoltaics, a subfield of organic photovoltaics (OPV), has attracted increasing interest in recent years due to the eco-friendly fabrication of solar modules afforded by colloidal ink technology. Importantly, using this approach it is now possible to engineer the microstructure of the light absorbing/charge generating layer of organic photovoltaics; decoupling film morphology from film deposition. In this study, single-component nanoparticles of poly(3-hexylthiophene) (P3HT) and phenyl-C 61 butyric acid methyl ester (PC 61 BM) were synthesized and used to generate a two-phase microstructure with control over domain size prior to film deposition. Scanning transmission X-ray microscopy (STXM) and electron microscopy were used to characterize the thin film morphology. Uniquely, the measured microstructure was a direct input for a nanoscopic kinetic Monte Carlo (KMC) model allowing us to assess exciton transport properties that are experimentally inaccessible in these single-component particles. Photoluminescence, UV-vis spectroscopy measurements, and KMC results of the nanoparticle thin films enabled the calculation of an experimental exciton dissociation efficiency (η ED ) of 37% for the two-phase microstructure. The glass transition temperature (T g ) of the materials was characterized with dynamic mechanical thermal analysis (DMTA) and thermal annealing led to an increase in ηED to 64% due to an increase in donor-acceptor interfaces in the thin film from both sintering of neighboring opposite-type particles in addition to the generation of a third mixed phase from diffusion of PC 61 BM into amorphous P3HT domains. Finally, this study demonstrates the higher level of control over donor-acceptor film morphology enabled by customizing nanoparticulate colloidal inks, where the optimal three-phase film morphology for an OPV photoactive layer can be designed and engineered.

36 MATERIALS SCIENCE↗

Sub-single exciton optical gain threshold in colloidal semiconductor quantum wells with gradient alloy shelling

Colloidal semiconductor quantum wells have emerged as a promising material platform for use in solution-processable lasers. However, applications relying on their optical gain suffer from nonradiative Auger decay due to multi-excitonic nature of light amplification in II-VI semiconductor nanocrystals. Here, we show sub-single exciton level of optical gain threshold in specially engineered CdSe/CdS@CdZnS core/crown@gradient-alloyed shell quantum wells. This sub-single exciton ensemble-averaged gain threshold of (Ng)≈ 0.84 (per particle) resulting from impeded Auger recombination, along with a large absorption cross-section of quantum wells, enables us to observe the amplified spontaneous emission starting at an ultralow pump fluence of ~ 800 nJ cm –2 , at least three-folds better than previously reported values among all colloidal nanocrystals. Finally, using these gradient shelled quantum wells, we demonstrate a vertical cavity surface-emitting laser operating at a low lasing threshold of 7.5 μJ cm –2 . These results represent a significant step towards the realization of solution-processable electrically-driven colloidal lasers.

36 MATERIALS SCIENCE↗

Ligand-Mediated Nucleation and Growth of Palladium Metal Nanoparticles

The size, size distribution and stability of colloidal nanoparticles are greatly affected by the presence of capping ligands. Despite the key contribution of capping ligands during the synthesis reaction, their role in regulating the nucleation and growth rates of colloidal nanoparticles is not well understood. In this work, we demonstrate a mechanistic investigation of the role of trioctylphosphine (TOP) in Pd nanoparticles in different solvents (toluene and pyridine) using in situ SAXS and ligand-based kinetic modeling. Our results under different synthetic conditions reveal the overlap of nucleation and growth of Pd nanoparticles during the reaction, which contradicts the LaMer-type nucleation and growth model. The model accounts for the kinetics of Pd-TOP binding for both, the precursor and the particle surface, which is essential to capture the size evolution as well as the concentration of particles in situ. In addition, we illustrate the predictive power of our ligand-based model through designing the synthetic conditions to obtain nanoparticles with desired sizes. The proposed methodology can be applied to other synthesis systems and therefore serves as an effective strategy for predictive synthesis of colloidal nanoparticles.

Mozaffari, Saeed↗

Ion beam analyses of radionuclide migration in heterogeneous rocks

The migration of radionuclides (RN) in the environment is a topic of general interest, for its implications on public health, and it is an issue for the long-term safety studies of deep geological repositories (DGR) for high-level radioactive waste. The role played by colloids on RN migration is also of great concern. Diffusion and sorption are fundamental mechanisms controlling RN migration in rocks and many experimental approaches are applied to determine transport parameters for low sorbing RN in homogeneous rocks. However, it is difficult to obtain relevant data for high sorbing RN or colloids, for which diffusion lengths are extremely short, or within heterogeneous rocks, where transport might be different in different minerals. The ion beam techniques Rutherford Backscattering Spectrometry (RBS) and micro-Particle Induced X-Ray Emission ({mu}PIXE), rarely applied in the field, were selected for their micro-analytical potential to study RN diffusion and surface retention within heterogeneous rocks. Main achievements obtained during last 12 years are highlighted.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗