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At least 163 records · Page 9

Printed Electrochemical Sensor for Quantifying Bone Density Loss in Microgravity

Printed electrochemical biosensors have been developed for astronaut point-of-care testing. Our fabrication approach is complimentary with in-space manufacturing for an on-demand and hands-free fabrication process. These sensors are developed using a combination of thin film materials printing and 3D printing and are comprised of carbon nanotube, gold nanoparticle, silver nanoparticle and dielectric inks to make traditional electrochemical sensor devices. Initial prototyped printed electrochemical sensors demonstrate good electrochemical performance while also displaying low batch to batch variability. Here we report the development of a printed sensor to monitor bone turnover. The absence of load bearing forces experienced in microgravity causes a reduction of overall bone mass and results in the development of space osteopenia/osteoporosis.(1,2) Our approach to identify space osteopenia/osteoporosis is to monitor the change in bone mass indirectly through an excreted biomarker of bone remodeling, amino-terminal collagen crosslinks (NTX). Antibodies specific to NTX are added to the sensor’s electrode ink and applied during the manufacturing process. NTX is measured from a urine sample by changes in voltammetry and electrochemical impedance as it binds to the antibody modified electrode surface. The measurement is rapid, quantitative and requires only small handheld electronics to perform the measurement. By this process, ground and flight physicians will receive frequent and real-time insight into the development of space osteopenia/osteoporosis to guide appropriate countermeasures. REFERENCES [1] Nabavi, N. et al (2011) Bone 49, 965-974. [2] Tamma, R. et al (2009) FASEB J 23, 2549-2554.

in-space manufacturing↗

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↗

Novel Materials, Processing and Device Technologies for Space Exploration with Potential Dual-Use Applications

We highlight results of a broad spectrum of efforts on lower-temperature processing of nanomaterials, novel approaches to energy conversion, and environmentally rugged devices. Solution-processed quantum dots of copper indium chalcogenide semiconductors and multiwalled carbon nanotubes from lower-temperature spray pyrolysis are enabled by novel (precursor) chemistry. Metal-doped zinc oxide (ZnO) nanostructured components of photovoltaic cells have been grown in solution at low temperature on a conductive indium tin oxide substrate. Arrays of ZnO nanorods can be templated and decorated with various semiconductor and metallic nanoparticles. Utilizing ZnO in a more broadly defined energy conversion sense as photocatalysts, unwanted organic waste materials can potentially be repurposed. Current efforts on charge carrier dynamics in nanoscale electrode architectures used in photoelectrochemical cells for generating solar electricity and fuels are described. The objective is to develop oxide nanowire-based electrode architectures that exhibit improved charge separation, charge collection and allow for efficient light absorption. Investigation of the charge carrier transport and recombination properties of the electrodes will aid in the understanding of how nanowire architectures improve performance of electrodes for dye-sensitized solar cells. Nanomaterials can be incorporated in a number of advanced higher-performance (i.e. mass specific power) photovoltaic arrays. Advanced technologies for the deposition of 4H-silicon carbide are described. The use of novel precursors, advanced processing, and process studies, including modeling are discussed from the perspective of enhancing the performance of this promising material for enabling technologies such as solar electric propulsion. Potential impact(s) of these technologies for a variety of aerospace applications are highlighted throughout. Finally, examples are given of technologies with potential spin-offs for dual-use or terrestrial applications.

solid state devices↗

Analysis of Crystallization Kinetics

A realistic computer model for polymorphic crystallization (i.e., initial and final phases with identical compositions), which includes time-dependent nucleation and cluster-size-dependent growth rates, is developed and tested by fits to experimental data. Model calculations are used to assess the validity of two of the more common approaches for the analysis of crystallization data. The effects of particle size on transformation kinetics, important for the crystallization of many systems of limited dimension including thin films, fine powders, and nanoparticles, are examined.

Kelton, Kenneth F.↗

The Features of Self-Assembling Organic Bilayers Important to the Formation of Anisotropic Inorganic Materials in Microgravity Conditions

There is a growing need for inorganic anisotropic particles in a variety of materials science applications. Structural, optical, and electrical properties can be greatly augmented by the fabrication of composite materials with anisotropic microstructures or with anisotropic particles uniformly dispersed in an isotropic matrix. Examples include structural composites, magnetic and optical recording media, photographic film, certain metal and ceramic alloys, and display technologies including flat panel displays. While considerable progress has been made toward developing an understanding of the synthesis of powders composed of monodispersed, spherical particles, these efforts have not been transferred to the synthesis of anisotropic nanoparticles. The major objective of the program is to develop a fundamental understanding of the growth of anisotropic particles at organic templates, with emphasis on the chemical and structural aspects of layered organic assemblies that contribute to the formation of anisotropic inorganic particles.

Talham, Daniel R.↗

Surface Plasmon Resonance Evaluation of Colloidal Metal Aerogel Filters

We have fabricated aerogels containing gold, silver, and platinum nanoparticles for gas catalysis applications. By applying the concept of an average or effective dielectric constant to the heterogeneous interlayer surrounding each particle, we extend the technique of immersion spectroscopy to porous or heterogeneous media. Specifically, we apply the predominant effective medium theories for the determination of the average fractional composition of each component in this inhomogeneous layer. Hence, the surface area of metal available for catalytic gas reaction is determined. The technique is satisfactory for statistically random metal particle distributions but needs further modification for aggregated or surfactant modified systems. Additionally, the kinetics suggest that collective particle interactions in coagulated clusters are perturbed during silica gelation resulting in a change in the aggregate geometry.

Smith, David D.↗

Z-Scan Measurement of the Nonlinear Absorption of a Thin Gold Film

We have used the z-scan technique at a wavelength (532 nm) near the transmission window of bulk gold to measure the nonlinear absorption coefficient of continuous approximately 50-Angstrom-thick gold films, deposited onto surface-modified quartz substrates. For highly absorbing media such as metals, we demonstrate that determination of either the real or imaginary part of the third-order susceptibility requires a measurement of both nonlinear absorption and nonlinear refraction, i.e. both open- and closed-aperture z-scans must be performed. Closed-aperture z-scans did not yield a sufficient signal for the determination of the nonlinear refraction. However, open-aperture z-scans yielded values ranging from Beta = 1.9 x 10(exp -3) to 5.3 x 10(exp -3) cm/W in good agreement with predictions which ascribe the nonlinear response to a Fermi smearing mechanism. We note that the sign of the nonlinearity is reversed from that of gold nanoparticle composites, in accordance with the predictions of mean field theories.

Smith, David D.↗

Noble Metal Immersion Spectroscopy of Silica Alcogels and Aerogels

We have fabricated aerogels containing gold and silver nanoparticles for gas catalysis applications. By applying the concept of an average or effective dielectric constant to the heterogeneous interlayer surrounding each particle, we extend the technique of immersion spectroscopy to porous or heterogeneous media. Specifically, we apply the predominant effective medium theories for the determination of the average fractional composition of each component in this inhomogeneous layer. Hence, the surface area of metal available for catalytic gas reaction is determined. The technique is satisfactory for statistically random metal particle distributions but needs further modification for aggregated or surfactant modified systems. Additionally, the kinetics suggest that collective particle interactions in coagulated clusters are perturbed during silica gelation resulting in a change in the aggregate geometry.

Smith, David D.↗

The Influence of Microgravity on Silica Sol-Gel Formation

We discuss space-flight experiments involving the growth of silica particles and gels. The effect of microgravity on the growth of silica particles via the sol-gel route is profound. In four different recipes spanning a large range of the parameter space that typically produces silica nanoparticles in unit-gravity, low-density gel structures were instead formed in microgravity. The particles that did form were generally smaller and more polydisperse than those grown on the ground. These observations suggest that microgravity reduces the particle growth rate, allowing unincorporated species to form aggregates and ultimately gel. Hence microgravity favors the formation of more rarefied structures, providing a bias towards diffusion-limited cluster-cluster aggregation. These results further suggest that in unit gravity, fluid flows and sedimentation can significantly perturb sol-gel substructures prior to gelation and these deleterious perturbations may be "frozen" into the resulting microstructure. Hence, sol-gel pores may be expected to be smaller, more uniform, and less rough when formed in microgravity.

Sibille, L.↗

Determination of a Two-Phase Structure of Nanocrystals: GaN and SiC

The properties of nano-crystalline materials are critically dependent on the structure of the constituent grains. Experimental conditions necessary to perform structural analysis of nanocrystalline materials as a two-phase core-surface shell system are discussed. It is shown, that a standard X-ray diffraction measurements and analysis are insufficient and may lead to incorrect conclusions as to the real structure of the materials. A new method of evaluation of powder diffraction data based on the analysis of the shift of the Bragg reflections from their perfect-lattice positions was developed. "Apparent lattice parameters" quantity, alp, was introduced and calculated from the actual positions of each individual Bragg reflection. The alp values plotted versus diffraction vector (Q) show characteristic features that are used for evaluation of the experimental results. The study was based on modeling of nano-grains and simulations of theoretical intensity profiles using the Debye functions. The method was applied to the analysis of synchrotron X-ray diffraction data of GaN and SiC nanocrystals. A presence of strained surface shell and a considerable internal pressure (GaN) in the nanoparticles was concluded.

Palosz, W.↗

Computer Simulation of the Forces Acting on the Polystyrene Probe Submerged into the Succinonitrile Near Phase Transition

Modeling approach to simulate both mesoscale and microscopic forces acting in a typical AFM experiment is presented. At mesoscale level interaction between the cantilever tip and the sample surface is primarily described by the balance of attractive Van der Waals and repulsive forces. The model of cantilever oscillations is applicable to both non-contact and "tapping" AFM. This model can be farther enhanced to describe nanoparticle manipulation by cantilever. At microscopic level tip contamination and details of tip-surface interaction can be simulated using molecular dynamics approach. Integration of mesoscale model with molecular dynamic model is discussed.

Bune, Andris V.↗

Flame Synthesis of Single- and Multi-Walled Carbon Nanotubes and Nanofibers

Metal-catalyzed carbon nanotubes are highly sought for a diverse range of applications that include nanoelectronics, battery electrode material, catalysis, hydrogen storage media and reinforcing agents in polymer composites. These latter applications will require vast quantities of nanotubes at competitive prices to be economically feasible. Moreover, reinforcing applications may not require ultrahigh purity nanotubes. Indeed, functionalization of nanotubes to facilitate interfacial bonding within composites will naturally introduce defects into the tube walls, lessening their tensile strength. Current methods of aerosol synthesis of carbon nanotubes include laser ablation of composite targets of carbon and catalyst metal within high temperature furnaces and decomposition of a organometallics in hydrocarbons mixtures within a tube furnace. Common to each approach is the generation of particles in the presence of the reactive hydrocarbon species at elevated temperatures. In the laser-ablation approach, the situation is even more dynamic in that particles and nanotubes are borne during the transient cooling phase of the laser-induced plasma for which the temperature far exceeds that of the surrounding hot gases within the furnace process tube. A shared limitation is that more efficient methods of nanoparticle synthesis are not readily incorporated into these approaches. In contrast, combustion can quite naturally create nanomaterials such as carbon black. Flame synthesis is well known for its commercial scalability and energy efficiency. However, flames do present a complex chemical environment with steep gradients in temperature and species concentrations. Moreover, reaction times are limited within buoyant driven flows to tens of milliseconds. Therein microgravity can greatly lessen temperature and spatial gradients while allowing independent control of flame residence times. In preparation for defining the microgravity experiments, the work presented here focuses on the effect of catalyst particle size and reactant gas in 1g.

VanderWal, R. L.↗

Cometary Science After Hale-Bopp

Comets and the chondritic porous interplanetary dust particles (CP IDPs) that they shed in their comae are reservoirs of primitive solar nebula materials. The high porosity and fragility of cometary grains and CP IDPs, and anomalously high deuterium contents of pyroxene-rich CP IDPs imply these aggregate particles contain significant interstellar grain components. Spectrophotometry of comets at thermal IR wavelengths (3-40 microns) reveal the presence of a warm (near-IR) featureless emission modeled by amorphous carbon grains, and mid-IR and far-IR broad and narrow resonances modeled by chondritic (50% Fe and 50% Mg) amorphous and Mg-rich crystalline silicate minerals, respectively. Cometary amorphous silicate resonances are well matched by IR spectra of CP IDPs dominated by 0.1 micron spherules of Glass with Embedded Metal and Sulfides (GEMS) that are thought to be the interstellar Fe-bearing amorphous silicates produced in the cooling outflows of Asymptotic Giant Branch (AGB) stars. Acid-etched microtomed CP IDP samples, however, show that both the carbon phase (aliphatic) and the amorphous silicate phase (Mg-rich) are not optically absorbing while the embedded Fe nanoparticles make the IDPs dark. The CP IDPs suggest either significant processing has occurred in the ISM or that the AGB amorphous silicates have Mg-rich stoichiometry and possibly grew on Fe particle condensates. Cometary crystalline silicate resonances are well matched by IR spectra of laboratory submicron Mg-rich olivine crystals, [Mg(sub y),Fe(sub 1-y)]2SiO4 with y/ge0.85, and in the case of Hale-Bopp at r(sub h) less than or equal to approx. 1.5 AU, by Mg-rich pyroxene crystals, [Mg(sub x),Fe(sub 1-x)]SiO3 with x/ge0.85. While a fraction of AGB stardust (less than or equal to 15%) are Mg-rich crystals, this interstellar star dust component is insufficient to account for the deduced abundance of crystalline minerals in comet dust. An insufficient source of ISM Mg-rich crystals leads to the inference that Mg-rich crystals in comets may be hot, early solar nebula condensates that traveled large radial distances out to the comet-forming zone.

Wooden, Diane H.↗

Carbon Nanotubes Growth on Graphite Fibers

Carbon nanotubes (CNT) were synthesized on graphite fibers by thermal Chemical Vapor Deposition (CVD). On the fiber surface, iron nanoparticles are coated and act as catalysts for CNT growth. The growth temperature ranges from 550 to 1000 C at an ambient pressure. Methane and hydrogen gases with methane contents of 10% to 100% are used for the CNT synthesis. At high growth temperatures (greater than 800 C), the rapid inter-diffusion of the transition metal iron on the graphite surface results in a rough fiber surface with no CNT grown on the surface. When the growth temperature is relatively low (650 - 800 C), CNT are fabricated on the graphite surface with catalytic particles on the nanotube top ends. Using micro Raman spectroscopy in the breath mode region, single-walled or multi-walled CNT can be determined, depending on methane concentrations.

Zhu, Shen↗

Carbon Nanotubes Growth by CVD on Graphite Fibers

Due to the superior electrical and mechanical properties of carbon nanotubes (CNT), synthesizing CNT on various substances for electronics devices and reinforced composites have been engaged in many efforts for applications. This presentation will illustrate CNT synthesized on graphite fibers by thermal CVD. On the fiber surface, iron nanoparticles as catalysts for CNT growth are coated. The growth temperature ranges from 600 to 1000 C and the pressure ranges from 100 Torr to one atmosphere. Methane and hydrogen gases with methane content of 10% to 100% are used for the CNT synthesis. At high growth temperatures (greater than or equal to 900 C), the rapid inter-diffusion of the transition metal iron on the graphite surface results in the rough fiber surface without any CNT grown on it. When the growth temperature is relative low (650-800 C), CNT with catalytic particles on the nanotube top ends are fabricated on the graphite surface. (Methane and hydrogen gases with methane content of 10% to 100% are used for the CNT synthesis.) (By measuring the samples) Using micro Raman spectroscopy in the breath mode region, single-walled or multi-walled CNT (MWCNT), depending on growth concentrations, are found. Morphology, length and diameter of these MWCNT are determined by scanning electron microscopy and Raman spectroscopy. The detailed results of syntheses and characterizations will be discussed in the presentation.

Zhu, Shen↗

Development of Novel Composite and Random Materials for Nonlinear Optics and Lasers

A qualitative model explaining sharp spectral peaks in emission of solid-state random laser materials with broad-band gain is proposed. The suggested mechanism of coherent emission relies on synchronization of phases in an ensemble of emitting centers, via time delays provided by a network of random scatterers, and amplification of spontaneous emission that supports the spontaneously organized coherent state. Laser-like emission from powders of solid-state luminophosphors, characterized by dramatic narrowing of the emission spectrum and shortening of emission pulses above the threshold, was first observed by Markushev et al. and further studied by a number of research groups. In particular, it has been shown that when the pumping energy significantly exceeds the threshold, one or several narrow emission lines can be observed in broad-band gain media with scatterers, such as films of ZnO nanoparticles, films of pi-conjugated polymers or infiltrated opals. The experimental features, commonly observed in various solid-state random laser materials characterized by different particle sizes, different values of the photon mean free path l*, different indexes of refraction, etc.. can be described as follows. (Liquid dye random lasers are not discussed here.)

Noginov, Mikhail↗

Quantum Dot Solar Cells

We have been investigating the synthesis of quantum dots of CdSe, CuInS2, and CuInSe2 for use in an intermediate bandgap solar cell. We have prepared a variety of quantum dots using the typical organometallic synthesis routes pioneered by Bawendi, et. al., in the early 1990's. However, unlike previous work in this area we have also utilized single-source precursor molecules in the synthesis process. We will present XRD, TEM, SEM and EDS characterization of our initial attempts at fabricating these quantum dots. Investigation of the size distributions of these nanoparticles via laser light scattering and scanning electron microscopy will be presented. Theoretical estimates on appropriate quantum dot composition, size, and inter-dot spacing along with potential scenarios for solar cell fabrication will be discussed.

Raffaelle, Ryne P.↗

Application of Powder Diffraction Methods to the Analysis of the Atomic Structure of Nanocrystals: The Concept of the Apparent Lattice Parameter (ALP)

The applicability of standard methods of elaboration of powder diffraction data for determination of the structure of nano-size crystallites is analysed. Based on our theoretical calculations of powder diffraction data we show, that the assumption of the infinite crystal lattice for nanocrystals smaller than 20 nm in size is not justified. Application of conventional tools developed for elaboration of powder diffraction data, like the Rietveld method, may lead to erroneous interpretation of the experimental results. An alternate evaluation of diffraction data of nanoparticles, based on the so-called 'apparent lattice parameter' (alp) is introduced. We assume a model of nanocrystal having a grain core with well-defined crystal structure, surrounded by a surface shell with the atomic structure similar to that of the core but being under a strain (compressive or tensile). The two structural components, the core and the shell, form essentially a composite crystal with interfering, inseparable diffraction properties. Because the structure of such a nanocrystal is not uniform, it defies the basic definitions of an unambiguous crystallographic phase. Consequently, a set of lattice parameters used for characterization of simple crystal phases is insufficient for a proper description of the complex structure of nanocrystals. We developed a method of evaluation of powder diffraction data of nanocrystals, which refers to a core-shell model and is based on the 'apparent lattice parameter' methodology. For a given diffraction pattem, the alp values are calculated for every individual Bragg reflection. For nanocrystals the alp values depend on the diffraction vector Q. By modeling different a0tomic structures of nanocrystals and calculating theoretically corresponding diffraction patterns using the Debye functions we showed, that alp-Q plots show characteristic shapes which can be used for evaluation of the atomic structure of the core-shell system. We show, that using a simple model of a nanocrystal with spherical shape and centro-symmetric strain at the surface shell we obtain theoretical alp-Q values which match very well the alp-Q plots determined experimentally for Sic, GaN, and diamond nanopowders. The theoretical models are defined by the lattice parameter of the grain core, thickness of the surface shell, and the magnitude and distribution of the strain field in the surface shell. According to our calculations, the part of the diffraction pattern measured at relatively low diffraction vectors Q (below 10/angstrom) provides information on the surface strain, whle determination of the lattice parameters in the grain core requires measurements at large Q-values (above 15 - 20/angstrom).

Palosz, B.↗