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At least 55 records · Page 3

Resonant surface enhancement of Raman scattering of Ag nanoparticles on silicon substrates fabricated by dc sputtering

Ag nanoparticles (AgNPs) were deposited onto silicon substrates by direct current (dc) magnetron sputtering. The influences of sputtering power and sputtering time on the AgNP film morphology were studied using atomic force microscopy. The particle size was successfully tuned from 19 nm to 53 nm by varying the sputtering time at a dc power of 10 W. When Rhodamine 6 G (R6G) was used as the probe molecule, the AgNP films showed significant surface enhanced Raman scattering effect. In particular, it is found that larger particles show stronger enhancement for lower concentrations of R6G while smaller particles display stronger enhancement for higher concentrations of R6G.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Topological defect dynamics in operando battery nanoparticles

Topological defects can markedly alter nanomaterial properties. This presents opportunities for "defect engineering," where desired functionalities are generated through defect manipulation. However, imaging defects in working devices with nanoscale resolution remains elusive. We report three-dimensional imaging of dislocation dynamics in individual battery cathode nanoparticles under operando conditions using Bragg coherent diffractive imaging. Dislocations are static at room temperature and mobile during charge transport. During the structural phase transformation, the lithium-rich phase nucleates near the dislocation and spreads inhomogeneously. The dislocation field is a local probe of elastic properties, and we find that a region of the material exhibits a negative Poisson's ratio at high voltage. Operando dislocation imaging thus opens a powerful avenue for facilitating improvement and rational design of nanostructured materials.

25 ENERGY STORAGE↗

Direct observation of metal nanoparticles as heterogeneous nuclei for the condensation of supersaturated organic vapors: Nucleation of size-selected aluminum nanoparticles in acetonitrile and n-hexane vapors

This work reports the direct observation and separation of size-selected aluminum nanoparticles acting as heterogeneous nuclei for the condensation of supersaturated vapors of both polar and nonpolar molecules. In the experiment, we study the condensation of supersaturated acetonitrile and n-hexane vapors on charged and neutral Al nanoparticles by activation of the metal nanoparticles to act as heterogeneous nuclei for the condensation of the organic vapor. Aluminum seed nanoparticles with diameters of 1 and 2 nm are capable of acting as heterogeneous nuclei for the condensation of supersaturated acetonitrile and hexane vapors. The comparison between the Kelvin and Fletcher diameters indicates that for the heterogeneous nucleation of both acetonitrile and hexane vapors, particles are activated at significantly smaller sizes than predicted by the Kelvin equation. The activation of the Al nanoparticles occurs at nearly 40% and 65% of the onset of homogeneous nucleation of acetonitrile and hexane supersaturated vapors, respectively. The lower activation of the charged Al nanoparticles in acetonitrile vapor is due to the charge-dipole interaction which results in rapid condensation of the highly polar acetonitrile molecules on the charged Al nanoparticles. The charge-dipole interaction decreases with increasing the size of the Al nanoparticles and therefore at low supersaturations, most of the heterogeneous nucleation events are occurring on neutral nanoparticles. No sign effect has been observed for the condensation of the organic vapors on the positively and negatively charged Al nanoparticles. The present approach of generating metal nanoparticles by pulsed laser vaporization within a supersaturated organic vapor allows for efficient separation between nucleation and growth of the metal nanoparticles and, consequently controls the average particle size, particle density, and particle size distribution within the liquid droplets of the condensing vapor. Strong correlation is found between the seed nanoparticle's size and the degree of the supersaturation of the condensing vapor. This result and the agreement among the calculated Kelvin diameters and the size of the nucleating Al nanoparticles determined by transmission electron microscopy provide strong proof for the development of a new approach for the separation and characterization of heterogeneous nuclei formed in organic vapors. These processes can take place in the atmosphere by a combination of several organic species including polar compounds which could be very efficient in activating charged nanoparticles and cluster ions of atmospheric relevance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Slowing of Femtosecond Laser-Generated Nanoparticles in a Background Gas

The slowing of Pt nanoparticles in argon background gas was characterized by Rayleigh scattering imaging using a plume of nanoparticles generated by femtosecond laser through thin film ablation (fs-TTFA) of 20 nanometers-thick Pt films. The ablation was performed at threshold laser energy fluences for complete film removal to provide a well-defined plume consisting almost entirely of nanoparticles traveling with a narrow velocity distribution, providing a unique system to unambiguously characterize the slowing of nanoparticles during interaction with background gases. Nanoparticles of ~200 nm diameter were found to decelerate in background Ar gas with pressures less than 50 Torr in good agreement with a linear drag model in the Epstein regime. Based on this model, the stopping distance of small nanoparticles in the plume was predicted and tested by particle collection in an off-axis geometry, and size distribution analysis by transmission electron microscopy. These results permit a basis to interpret nanoparticle propagation through background gases in laser ablation plumes that contain mixed components.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

The interfacial orientation relationship of oxide nanoparticles in a hafnium-containing oxide dispersion-strengthened austenitic stainless steel

This work reports comprehensive investigations on the orientation relationship of the oxide nanoparticles in a hafnium-containing austenitic oxide dispersion-strengthened 316 stainless steel. The phases of the oxide nanoparticles were determined by a combination of scanning transmission electron microscopy–electron dispersive X-ray spectroscopy, atom probe tomography and synchrotron X-ray diffraction to be complex Y–Ti–Hf–O compounds with similar crystal structures, including bixbyite Y{sub 2}O{sub 3}, fluorite Y{sub 2}O{sub 3}–HfO{sub 2} solid solution and pyrochlore (or fluorite) Y{sub 2}(Ti,Hf){sub 2−x}O{sub 7−x}. High resolution transmission electron microscopy was used to characterize the particle–matrix interfaces. Two different coherency relationships along with one axis-parallel relation between the oxide nanoparticles and the steel matrix were found. The size of the nanoparticles significantly influences the orientation relationship. The results provide insight into the relationship of these nanoparticles with the matrix, which has implications for interpreting material properties as well as responses to radiation. - Highlights: • The oxide nanoparticles in a hafnium-containing austenitic ODS were characterized. • The nanoparticles are Y–Hf–Ti–O enriched phases according to APT and STEM–EDS. • Two coherency and an axis-parallel orientation relationships were found by HR-TEM. • Particle size has a prominent effect on the orientation relationship (OR). • Formation mechanism of the oxide nanoparticles was discussed based on the ORs.

36 MATERIALS SCIENCE↗

Metabolism, Survival, and Gene Expression of Pseudomonas putida to Hematite Nanoparticles Mediated by Surface-Bound Humic Acid

Natural organic matter (NOM) is likely to coat naturally occurring nanoparticles (NNPs) in the soil environment and poses distinct effects on the interaction between NPs and soil microorganisms, however such topic has not been well investigated. This study explored the influence of nanoparticle surface-bound humic acid (HA, as a model NOM) on the toxicity of hematite NPs (i.e., nano-Fe2O3) to Pseudomonas putida (P. putida). Results showed that nano-Fe2O3 could inhibit the bacterial growth with an IC50 of 23.58 mg L-1, while nanoparticle surface-bound HA could significantly alleviate the P. putida toxicity of nano-Fe2O3. IC50 of nano-Fe2O3 increased to 4774.23 mg L-1 as a result of surface-saturation by HA. Co-precipitation experiment and transmission electron microscopy observation revealed that nanoparticle surface-bound HA prevented the adhesion of nano-Fe2O3 to the cells as well as limited cell internalization of nanoparticles due to the increased electrostatic repulsion. The generation of intracellular reactive oxygen species (ROS) was significantly limited by the nanoparticle surface-bound HA. The prevention of adhesion and inhibition of ROS generation could account for the HA-mitigated nanotoxicity. Interfacial interactions between hematite NPs and cell membrane were also evaluated on the basis of the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, and the magnitude of interaction energy barrier correlated well with the 48 h LC50 data of hematite NPs to P. putida. This result implies that metal oxide NPs with strong association with the cell surface might induce more severe cytotoxicity in microorganisms.

natural occurring nanoparticles, na, hematite, su,↗

Formation of Ge nanoparticles in SiO{sub x}N{sub y} by ion implantation and thermal annealing

Germanium nanoparticles embedded within dielectric matrices hold much promise for applications in optoelectronic and electronic devices. Here we investigate the formation of Ge nanoparticles in amorphous SiO{sub 1.67}N{sub 0.14} as a function of implanted atom concentration and thermal annealing temperature. Using x-ray absorption spectroscopy and other complementary techniques, we show Ge nanoparticles exhibit significant finite-size effects such that the coordination number decreases and structural disorder increases as the nanoparticle size decreases. While the composition of SiO{sub 1.67}N{sub 0.14} is close to that of SiO{sub 2}, we demonstrate that the addition of this small fraction of N yields a much reduced nanoparticle size relative to those formed in SiO{sub 2} under comparable implantation and annealing conditions. We attribute this difference to an increase in an atomic density and a much reduced diffusivity of Ge in the oxynitride matrix. These results demonstrate the potential for tailoring Ge nanoparticle sizes and structural properties in the SiO{sub x}N{sub y} matrices by controlling the oxynitride stoichiometry.

36 MATERIALS SCIENCE↗

The role of interfacial metal silicates on the magnetism in FeCo/SiO{sub 2} and Fe{sub 49%}Co{sub 49%}V{sub 2%}/SiO{sub 2} core/shell nanoparticles

We have investigated the role of spontaneously formed interfacial metal silicates on the magnetism of FeCo/SiO{sub 2} and Fe{sub 49%}Co{sub 49%}V{sub 2%}/SiO{sub 2} core/shell nanoparticles. Element specific x-ray absorption and photoelectron spectroscopy experiments have identified the characteristic spectral features of metallic iron and cobalt from within the nanoparticle core. In addition, metal silicates of iron, cobalt, and vanadium were found to have formed spontaneously at the interface between the nanoparticle core and silica shell. X-ray magnetic circular dichroism experiments indicated that the elemental magnetism was a result of metallic iron and cobalt with small components from the iron, cobalt, and vanadium silicates. Magnetometry experiments have shown that there was no exchange bias loop shift in the FeCo nanoparticles; however, exchange bias from antiferromagnetic vanadium oxide was measured in the V-doped nanoparticles. These results showed clearly that the interfacial metal silicates played a significant role in the magnetism of these core/shell nanoparticles, and that the vanadium percolated from the FeCo-cores into the SiO{sub 2}-based interfacial shell.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Influence of nanoparticle-ion and nanoparticle-polymer interactions on ion transport and viscoelastic properties of polymer electrolytes

We use atomistic simulations to probe the ion conductivities and mechanical properties of polyethylene oxide electrolytes containing Al{sub 2}O{sub 3} nanoparticles. We specifically study the influence of repulsive polymer-nanoparticle and ion-nanoparticle interactions and compare the results with those reported for electrolytes containing the polymorph β-Al{sub 2}O{sub 3} nanoparticles. We observe that incorporating repulsive nanoparticle interactions generally results in increased ionic mobilities and decreased elastic moduli for the electrolyte. Our results indicate that both ion transport and mechanical properties are influenced by the polymer segmental dynamics in the interfacial zones of the nanoparticle in the ion-doped systems. Such effects were seen to be determined by an interplay between the nanoparticle-polymer, nanoparticle-ion, and ion-polymer interactions. In addition, such interactions were also observed to influence the number of dissociated ions and the resulting conductivities. Within the perspective of the influence of nanoparticles on the polymer relaxation times in ion-doped systems, our results in the context of viscoelastic properties were consistent with the ionic mobilities. Overall, our results serve to highlight some issues that confront the efforts to use nanoparticle dispersions to simultaneously enhance the conductivity and the mechanical strength of polymer electrolyte.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Versatile Approach for Quantification of Surface Site Fractions using Reaction Kinetics: The Case of CO Oxidation on Supported Ir Single Atoms and Nanoparticles

Supported metal single atom catalysts have shown unique activity and selectivity for several reactions. Investigating the reaction mechanism on single atom catalysts and unambiguous assignment of the activity and selectivity requires catalysts with exclusively single atoms. However, it is challenging to prepare pure single atom catalysts with conventional impregnation methods, which typically result in a mixture of single atoms and nanoparticles. Here, we show that owing to different reaction mechanisms on single atoms and nanoparticles, reaction kinetics can serve as a surface sensitive characterization technique for quantifying their surface site fractions. As a case study, we use CO oxidation kinetics on Ir/MgAl2O4 to quantify the surface site fractions of single atoms and nanoparticles and the results are consistent with aberration-corrected scanning transmission electron microscopy, X-ray absorption fine structure and infrared spectroscopies. Additionally, by carefully choosing the reaction conditions, the activity of single atoms (or nanoparticles) can be made dominant, enabling detection of a small fraction, or allowing a study of their reaction mechanism on a catalyst containing a mixture of single atoms and nanoparticles. These results are general and could be applied to other systems where two types of sites have different reaction mechanisms.

Single atom catalyst, Kinetics, CO oxidation, x-ra↗

Synthesis and enhanced light absorption of alumina matrix nanocomposites containing multilayer oxide nanorods and silver nanoparticles

Highlights: {yields} Multilayer oxide nanorods (nanocables) were obtained via chemical processing. {yields} Ag nanoparticles were deposited between the core and shell layers of the nanorods. {yields} The structure and composition of the nanorods were analyzed by SEM and TEM. {yields} CoO nanorods and Ag nanoparticles enhance light absorption of the nanocomposites. -- Abstract: In this paper, multilayer oxide nanorods were deposited in the nanopores of anodic aluminum oxide (AAO) via solution infiltration followed by heat treatment. The nanorods have a core-shell structure. First, the shell (nanotube) with the thickness of about 40 nm was made of TiO{sub 2} through the hydrolysis of (NH{sub 4}){sub 2}TiF{sub 6}. Second, silver nanoparticles with the diameter of about 3 nm were added into the TiO{sub 2} layer through thermal decomposition of AgNO{sub 3} at elevated temperatures. Then, cylindrical cores (nanorods) of CoO and ZnO with 200 nm diameter were prepared, respectively. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the structure and composition of the nanorods. UV-vis light absorption measurements in the wavelength range from 350 to 1000 nm were performed to study the effect of nanorod and nanoparticle addition on the light absorption property of the alumina nanocomposites. It is found that CoO nanorods increase the light absorption of the alumina matrix composite in the wavelength range from 500 nm to 800 nm, but the TiO{sub 2} shell does not increase the light absorption much. The ZnO nanorods do not change the light absorption either. However, the addition of silver nanoparticles significantly enhances light absorption of both AAO/TiO{sub 2}/Ag/CoO and AAO/TiO{sub 2}/Ag/ZnO nanocomposites. This increase in the visible light absorption reveals that there exists surface plasmon around the fine silver nanoparticles in the nanorods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observing the colloidal stability of iron oxide nanoparticles in situ

Colloidal processes such as nucleation, growth, ripening, and dissolution are fundamental to the synthesis and application of engineered nanoparticles, as well as numerous natural systems. In nanocolloids consisting of a dispersion of nanoparticles in solution, colloidal stability is in?uenced by factors including the particle surface facet and capping layer, and local temperature, chemistry, and acidity. In this paper, we investigate colloidal stability through the real-time manipulation of nanoparticles using in situ liquid cell Scanning Transmission Electron Microscopy (STEM). In a distribution of uniform iron oxide nanoparticles, we use the electron beam to precisely control the local chemistry of the solution and observe the critical role that surface chemistry plays in nanoparticle stability. By functionalizing the nanoparticle surfaces with charged amino acids and peptides, stability can be tuned to promote dissolution, growth, or agglomeration, either permanently or reversibly. STEM imaging is used to quantify kinetics of individual nanoparticles subject to local variations in chemistry. These measurements of dissolution and growth rates of iron oxide nanoparticles provide insights into nanoparticle stability relevant to synthesis and functionalization for biomedical applications.

Hufschmid, Ryan D.↗

Zero-Valent Iron: Impact of Anions Present during Synthesis on Subsequent Nanoparticle Reactivity

Zero-valent iron particles are an effective remediation technology for ground water contaminated with halogenated organic compounds. In particular, nanoscale zero-valent iron is a promising material for remediation because of its high specific surface area, which results in faster rate constants and more effective use of the iron. An aspect of iron nanoparticle reactivity that has not been explored is the impact of anions present during iron metal nanoparticle synthesis. Solutions containing chloride, phosphate, sulfate, and nitrate anions and ferric ions were used to generate iron oxide nanoparticles. The resulting materials were dialyzed to remove dissolved by-products and then dried and reduced by hydrogen gas at high temperature. The reactivity of the resulting zero-valent iron nanoparticles was quantified by monitoring the kinetics as well as products of carbon tetrachloride reduction, and significant differences in reactivity and chloroform yield were observed. The reactivity of nanoparticles prepared in the presence of sulfate and phosphate demonstrated the highest reactivity and chloroform yield. Furthermore, substantial variations in the solid-state products of oxidation (magnetite, iron sulfide, goethite, etc.) were also observed.

42 ENGINEERING↗

Studies on the chemical synthesis and characterization of lead oxide nanoparticles with different organic capping agents

Lead oxide (PbO) nanoparticles were chemically synthesized using Lead (II) acetate as precursor. The effects of organic capping agents such as Oleic acid, Ethylene Diamine Tetra Acetic acid (EDTA) and Cetryl Tri Methyl Butoxide (CTAB) on the size and morphology of the nanoparticles were studied. Characterization techniques such as X-ray diffraction (XRD), Fourier Transform-Infrared spectroscopy (FT-IR), Photoluminescence (PL) Field Emission Scanning Electron Microscopy (FE-SEM), Energy Dispersive Spectroscopy (EDS) and Transmission Electron Microscopy (TEM) were used to analyse the prepared nanoparticles for their physical, structural and optical properties. The characterization studies reveal that the synthesized PbO nanoparticles had well defined crystalline structure and sizes in the range of 25 nm to 36 nm for capping agents used and 40 nm for pure PbO nanoparticles.

36 MATERIALS SCIENCE↗