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At least 19 records

Synthesis of Graphite Encapsulated Metal Nanoparticles and Metal Catalyzed Nanotubes

This work focuses on the growth and inception of graphite encapsulated metal nanoparticles and metal catalyzed nanotubes using combustion chemistry. Deciphering the inception and growth mechanism(s) for these unique nanostructures is essential for purposeful synthesis. Detailed knowledge of these mechanism(s) may yield insights into alternative synthesis pathways or provide data on unfavorable conditions. Production of these materials is highly desirable given many promising technological applications.

vanderWal, R. L.

Carbon Materials Embedded with Metal Nanoparticles as Anode in Lithium-Ion Batteries

Carbon materials containing metal nanoparticles that can form an alloy with lithium were tested for their capacity and cycle life to store and release lithium electrochemically. Metal nanoparticles may provide the additional lithium storage capacity as well as additional channels to conduct lithium in carbon. The cycle life of this carbon-metal composite can be long because the solid-electrolyte interface (SEI) on the carbon surface may protect both lithium and the metal particles in the carbon interior. In addition, the voids in the carbon interior may accommodate the nanoparticle's volume change, and such volume change may not cause much internal stress due to small sizes of the nanoparticles. This concept of improving carbon's performance to store and release lithium was demonstrated using experimental cells of C(Pd)/0.5M Lil-50/50 (vol.%) EC and DMC/Li, where C(Pd) was graphitized carbon fibers containing palladium nanoparticles, EC was ethylene carbonate, and DMC was dimethyl carbonate. However, such improvement was not observed if the Pd nanoparticles are replaced by aluminum, possibly because the aluminum nanoparticles were oxidized in air during storage, resulting in an inert oxide of aluminum. Further studies are needed to use this concept for practical applications.

Hung, Ching-cheh

Thermoelectric Performance Enhancement by Surrounding Crystalline Semiconductors with Metallic Nanoparticles

Direct conversion of thermal energy to electricity by thermoelectric (TE) devices may play a key role in future energy production and utilization. However, relatively poor performance of current TE materials has slowed development of new energy conversion applications. Recent reports have shown that the dimensionless Figure of Merit, ZT, for TE devices can be increased beyond the state-of-the-art level by nanoscale structuring of materials to reduce their thermal conductivity. New morphologically designed TE materials have been fabricated at the NASA Langley Research Center, and their characterization is underway. These newly designed materials are based on semiconductor crystal grains whose surfaces are surrounded by metallic nanoparticles. The nanoscale particles are used to tailor the thermal and electrical conduction properties for TE applications by altering the phonon and electron transport pathways. A sample of bismuth telluride decorated with metallic nanoparticles showed less thermal conductivity and twice the electrical conductivity at room temperature as compared to pure Bi2Te3. Apparently, electrons cross easily between semiconductor crystal grains via the intervening metallic nanoparticle bridges, but phonons are scattered at the interfacing gaps. Hence, if the interfacing gap is larger than the mean free path of the phonon, thermal energy transmission from one grain to others is reduced. Here we describe the design and analysis of these new materials that offer substantial improvements in thermoelectric performance.

Kim, Hyun-Jung

Tunable Optical Properties of Metal Nanoparticle Sol-Gel Composites

We demonstrate that the linear and non-linear optical properties of sol-gels containing metal nanoparticles are highly tunable with porosity. Moreover, we extend the technique of immersion spectroscopy to inhomogeneous hosts, such as aerogels, and determine rigorous bounds for the average fractional composition of each component, i.e., the porosity of the aerogel, or equivalently, for these materials, the catalytic dispersion. Sol-gels containing noble metal nanoparticles were fabricated and a significant blue-shift in the surface plasmon resonance (SPR) was observed upon formation of an aerogel, as a result of the decrease in the dielectric constant of the matrix upon supercritical extraction of the solvent. However, as a result of chemical interface damping and aggregation this blue-shift does not strictly obey standard effective medium theories. Mitigation of these complications is achieved by avoiding the use of alcohol and by annealing the samples in a reducing atmosphere.

Smith, David D.

Fabrication of Metallic Hollow Nanoparticles

Metal and semiconductor nanoshells, particularly transition metal nanoshells, are fabricated using dendrimer molecules. Metallic colloids, metallic ions or semiconductors are attached to amine groups on the dendrimer surface in stabilized solution for the surface seeding method and the surface seedless method, respectively. Subsequently, the process is repeated with additional metallic ions or semiconductor, a stabilizer, and NaBH.sub.4 to increase the wall thickness of the metallic or semiconductor lining on the dendrimer surface. Metallic or semiconductor ions are automatically reduced on the metallic or semiconductor nanoparticles causing the formation of hollow metallic or semiconductor nanoparticles. The void size of the formed hollow nanoparticles depends on the dendrimer generation. The thickness of the metallic or semiconductor thin film around the dendrimer depends on the repetition times and the size of initial metallic or semiconductor seeds.

Kim, Jae-Woo

Metal Nanoparticle Catalysts for Carbon Nanotube Growth

Work this summer involved and new and unique process for producing the metal nanoparticle catalysts needed for carbon nanotube (CNT) growth. There are many applications attributed to CNT's, and their properties have deemed them to be a hot spot in research today. Many groups have demonstrated the versatility in CNT's by exploring a wide spectrum of roles that these nanotubes are able to fill. A short list of such promising applications are: nanoscaled electronic circuitry, storage media, chemical sensors, microscope enhancement, and coating reinforcement. Different methods have been used to grow these CNT's. Some examples are laser ablation, flame synthesis, or furnace synthesis. Every single approach requires the presence of a metal catalyst (Fe, Co, and Ni are among the best) that is small enough to produce a CNT. Herein lies the uniqueness of this work. Microemulsions (containing inverse micelles) were used to generate these metal particles for subsequent CNT growth. The goal of this summer work was basically to accomplish as much preliminary work as possible. I strived to pinpoint which variable (experimental process, metal product, substrate, method of application, CVD conditions, etc.) was the determining factor in the results. The resulting SEM images were sufficient for the appropriate comparisons to be made. The future work of this project consists of the optimization of the more promising experimental procedures and further exploration onto what exactly dictated the results.

Pierce, Benjamin F.

Plasmon Resonances of Metal Nanoparticles in an Absorbing Medium

We study the behavior of plasmon resonances of metal nanospheres embedded in an absorbing medium. First-principles far-field computations based on the general Lorenz–Mie theory show that increasing absorption in the host medium broadens and suppresses plasmon resonances in the extinction and effective scattering efficiency factors and suppresses resonance features in the phase function. These effects of absorption are analogous to those on the morphology-dependent resonances of dielectric particles with large size parameters.

Mishchenko, Michael I.

Metal Nanoparticle Aerogel Composites

We have fabricated sol-gels containing gold and silver nanoparticles. Formation of an aerogel produces a blue shift in the surface plasmon resonance as a result of the decrease in the dielectric constant of the matrix upon supercritical extraction of the solvent. However, as a result of chemical interface damping this blue shift does not obey effective medium theories. Annealing the samples in a reducing atmosphere at 400 C eliminates this discrepancy and results in narrowing and further blue shifting of the plasmon resonance. Metal particle aggregation also results in a deviation from the predictions of effective medium theories, but can be controlled through careful handling and by avoiding the use of alcohol. By applying effective medium theories to the heterogeneous interlayer surrounding each metal particle, we extend the technique of immersion spectroscopy to inhomogeneous materials characterized by spatially dependent dielectric constants, such as aerogels. We demonstrate that the shift in the surface plasmon wavelength provides the average fractional composition of each component (air and silica) in this inhomogeneous layer, i.e. the porosity of the aerogel or equivalently, for these materials, the catalytic dispersion. Additionally, the kinetics suggest that collective particle interactions in coagulated metal clusters are perturbed during silica gelation resulting in a change in the aggregate geometry.

Smith, David D.

Synthesis of Metal Nanoparticle-decorated Carbon Nanotubes under Ambient Conditions

This viewgraph presentation reviews the production of Metal Nanoparticle-decorated carbon Nanotubes. Multi-walled carbon nanotubes (MWCNTs) were efficiently decorated with metal nanoparticles (e.g. Ag, Pt, etc.) using the corresponding metal acetate in a simple mixing process without the need of chemical reagents or further processing. The conversion of acetate compounds to the corresponding metal reached over 90%, forming nanoparticles with average diameters less than 10 nm under certain conditions. The process was readily scalable allowing for the convenient preparation of multi-gram quantities of metal nanoparticle-decorated MWCNTs in a matter of a few minutes. These materials are under evaluation for a variety of electrical and catalytic applications. The preparation and characterization of these materials will be presented. The microscopic views of the processed MWCNTs are shown

Lin, Yi

Carbon Nanotube Synthesis in a Flame with Independently Prepared Laser-Ablated Catalyst Particles

Laser ablation has been used ex situ to create metal nanoparticles for introduction into a reactive pyrolysis flame. By prior synthesis of the metal nanoparticles, the effects of the reactive gases can be clearly separated from the pyrolysis chemistry of a solvent carrier, as when nebulized solutions are used. Moreover, varying reactivity issues associated with particle growth and size are bypassed. Our results show that Fe selectively reacts with CO to produce nanotubes, whereas Ni selectively reacts with C2H2 to produce nanofibers. These observations are interpreted through the donation and withdrawal of electron density between the adsorbate's molecular orbitals and surface atoms of the metal nanoparticle. The rate of reaction of Ni with only C2H2 is found to be greater than the rate with C2H2 and CO. This suggests that CO inhibits the Ni-catalyzed reaction.

Nanotubes, Carbon/chemistry/ultrastructure

Surface Plasmon Resonance Evaluation of Colloidal Metal Aerogel Filters

Surface plasmon resonance imaging has in the past been applied to the characterization of thin films. In this study we apply the surface plasmon technique not to determine macroscopic spatial variations but rather to determine average microscopic information. Specifically, we deduce the dielectric properties of the surrounding gel matrix and information concerning the dynamics of the gelation process from the visible absorption characteristics of colloidal metal nanoparticles contained in aerogel pores. We have fabricated aerogels containing gold and silver nanoparticles. Because the dielectric constant of the metal particles is linked to that of the host matrix at the surface plasmon resonance, any change 'in the dielectric constant of the material surrounding the metal nanoparticles results in a shift in the surface plasmon wavelength. During gelation the surface plasmon resonance shifts to the red as the average or effective dielectric constant of the matrix increases. Conversely, formation of an aerogel or xerogel through supercritical extraction or evaporation of the solvent produces a blue shift in the resonance indicating a decrease in the dielectric constant of the matrix. From the magnitude of this shift we deduce the average fraction of air and of silica in contact with the metal particles. The surface area of metal available for catalytic gas reaction may thus be determined.

Smith, David D.

Glass Frit Filters for Collecting Metal Oxide Nanoparticles

Filter disks made of glass frit have been found to be effective as means of high-throughput collection of metal oxide particles, ranging in size from a few to a few hundred nanometers, produced in gas-phase condensation reactors. In a typical application, a filter is placed downstream of the reactor and a valve is used to regulate the flow of reactor exhaust through the filter. The exhaust stream includes a carrier gas, particles, byproducts, and unreacted particle-precursor gas. The filter selectively traps the particles while allowing the carrier gas, the byproducts, and, in some cases, the unreacted precursor, to flow through unaffected. Although the pores in the filters are much larger than the particles, the particles are nevertheless trapped to a high degree: Anecdotal information from an experiment indicates that 6-nm-diameter particles of MnO2 were trapped with greater than 99-percent effectiveness by a filtering device comprising a glass-frit disk having pores 70 to 100 micrometer wide immobilized in an 8-cm-diameter glass tube equipped with a simple twist valve at its downstream end.

Ackerman, John

Conductive Carbon Nanotube Inks for Use with Desktop Inkjet Printing Technology

Inkjet printing is a common commercial process. In addition to the familiar use in printing documents from computers, it is also used in some industrial applications. For example, wire manufacturers are required by law to print the wire type, gauge, and safety information on the exterior of each foot of manufactured wire, and this is typically done with inkjet or laser printers. The goal of this work was the creation of conductive inks that can be applied to a wire or flexible substrates via inkjet printing methods. The use of inkjet printing technology to print conductive inks has been in testing for several years. While researchers have been able to get the printing system to mechanically work, the application of conductive inks on substrates has not consistently produced adequate low resistances in the kilohm range. Conductive materials can be applied using a printer in single or multiple passes onto a substrate including textiles, polymer films, and paper. The conductive materials are composed of electrical conductors such as carbon nanotubes (including functionalized carbon nanotubes and metal-coated carbon nanotubes); graphene, a polycyclic aromatic hydrocarbon (e.g., pentacene and bisperipentacene); metal nanoparticles; inherently conductive polymers (ICP); and combinations thereof. Once the conductive materials are applied, the materials are dried and sintered to form adherent conductive materials on the substrate. For certain formulations, increased conductivity can be achieved by printing on substrates supported by low levels of magnetic field alignment. The adherent conductive materials can be used in applications such as damage detection, dust particle removal, smart coating systems, and flexible electronic circuitry. By applying alternating layers of different electrical conductors to form a layered composite material, a single homogeneous layer can be produced with improved electrical properties. It is believed that patterning alternate layers of different conductors may improve electrical pathways through alignment of the conductors and band gap optimization. One feature of this innovation is that flexible conductive traces could be accomplished with a conductive ink having a surface resistivity of less than 10 ohms/square. Another result was that a composite material comprising a mixture of carbon nanotubes and metallic nanoparticles could be applied by inkjet printing to flexible substrates, and the resulting applied material was one to two orders of magnitude more conductive than a material made by printing inks containing carbon nanotubes alone.

Roberson, Luke

Metal-doped semiconductor nanoparticles and methods of synthesis thereof

The present invention generally relates to binary or higher order semiconductor nanoparticles doped with a metallic element, and thermoelectric compositions incorporating such nanoparticles. In one aspect, the present invention provides a thermoelectric composition comprising a plurality of nanoparticles each of which includes an alloy matrix formed of a Group IV element and Group VI element and a metallic dopant distributed within the matrix.

Ren, Zhifeng

Print-Consistency and Process-Interaction for Inkjet-Printed Copper on Flexible Substrate

Printed electronics is a fastest growing and emerging technology that have shown much potential in several industries including automotive, wearables, healthcare, and aerospace. Its applications can be found not only in flexible but also in large area electronics. The technology provides an effective and convenient method to additively deposit conductive and insulating materials on any type of substrate. Comparing with traditional manufacturing processes, which involves chemical etching, this technology also comes to be relatively environmental friendly. Despite its status, it is not without its challenges. Starting from the material being compatible in the printer equipment to the point of achieving fine resolutions, and with excellent properties are some of the challenges that printed electronics face. Among the myriad of printing technologies such as Aerosol Jet, micro-dispensing, gravure printing, screen printing, Inkjet printing, Inkjet has gained much attention due to its low-cost, low material consumption, and roll-to-roll capability for mass manufacturing. The technology has been widely used in home and office, but recently gained interest in printed electronics in a research and development setting. Conductive materials used in Inkjet printing generally comprises of metal Nanoparticles that need to be thermally sintered for it to be conductive. The preferred metal of choice has been mostly silver due to its excellent electrical properties and ease in sintering. However, silver comes to be expensive than its counterpart copper. Since copper is prone to oxidation, much focus has been given towards photonic sintering that involves sudden burst of pulsed light at certain energy to sinter the copper Nanoparticles. With this technique, only the printed material gets sintered in a matter of seconds without having a great impact on its substrate, due to which it is also preferred in low temperature applications. With all the knowledge, there is still a large gap in the process side with copper where it is important to look how the print process affects the resolution of the print along with the effect of post-print processes on electrical and mechanical properties. In this paper, a copper Inkjet ink is utilized for understanding the effect of Inkjet print parameters on the ejected droplet and its resolution. Post-print process is also quantified using a photonic sintering equipment for excellent electrical and mechanical properties. To demonstrate the complete process, commercial-off-the-shelf components will also be mounted on the additively printed pads via Inkjet. Statistically, control charting technique will be utilized to understand the capability of the Inkjet process.

printed electronics

Transmission Measurement of the Third-Order Susceptibility of Gold

Gold nanoparticle composites are known to display large optical nonlinearities. In order to assess the validity of generalized effective medium theories (EMT's) for describing the linear and nonlinear optical properties of metal nanoparticle composites, knowledge of the linear and nonlinear susceptibilities of the constituent materials is a prerequisite. In this study the inherent nonlinearity of the metal is measured directly (rather than deduced from a suitable EMT) using a very thin gold film. Specifically, we have used the z-scan technique at a wavelength near the transmission window of bulk gold to measure the third-order susceptibility of a continuous thin gold film deposited on a quartz substrate surface-modified with a self-assembled monolayer to promote adhesion and uniformity without affecting the optical properties. We compare our results with predictions which ascribe the nonlinear response to a Fermi-smearing mechanism. Further, we note that the sign of the nonlinear susceptibility is reversed from that of gold nanoparticle composites.

Smith, David D.