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At least 109 records · Page 6

Millimeter wave transmission studies of YBa2Cu3O7-delta thin films in the 26.5 to 40.0 GHz frequency range

Millimeter wave transmission measurements through YBa2Cu3O(7-delta) thin films on MgO, ZrO2 and LaAlO3 substrates, are reported. The films (approx. 1 micron) were deposited by sequential evaporation and laser ablation techniques. Transition temperatures T sub c, ranging from 89.7 K for the Laser Ablated film on LaAlO3 to approximately 72 K for the sequentially evaporated film on MgO, were obtained. The values of the real and imaginary parts of the complex conductivity, sigma 1 and sigma 2, are obtained from the transmission data, assuming a two fluid model. The BCS approach is used to calculate values for an effective energy gap from the obtained values of sigma sub 1. A range of gap values from 2 DELTA o/K sub B T sub c = 4.19 to 4.35 was obtained. The magnetic penetration depth is evaluated from the deduced values of sigma 2. These results are discussed together with the frequency dependence of the normalized transmission amplitude, P/P sub c, below and above T sub c.

Miranda, F. A.↗

Progress in Laser Based Carbon Nanotube Production and In-Situ Diagnostics at NASA/JSC

This paper focuses on the improvement of carbon nanotube production with the upgraded laser system operating at 60 Hz. The yield has increased by about five times with the new system, while the quality of the single wall nanotube (SWNT) is unchanged. Recent diagnostic data of spatial and temporal evolution of C2 in the laser ablation plume are obtained by imaging the plume area on a gated change coupled device. A three-laser setup is used to monitor nickel atoms in different parts of the plume by laser induced fluorescence (LIF). Measurements are made at different times after the ablating lasers. These results, along with the previous measurements of emission and LIF of C2 will be discussed. Our ultimate goal is to use these measurements to model the nanotube growth mechanism.

Arepalli, Sivaram↗

Using the Potassium-Argon Laser Experiment (KArLE) to Date Ancient, Low-K Chondritic Meteorites

Several laboratories have been investigating the feasibility of in situ K-Ar dating for use in future landing planetary missions. One drawback of these laboratory demonstrations is the insufficient analogy of the analyzed analog samples with expected future targets. We present the results obtained using the K-Ar laser experiment (KArLE) on two old and K-poor chondritic samples, Pułtusk and Hvittis, as better lunar analogs. The KArLE instrument uses laser ablation to vaporize rock samples and quantifies K content by laser-induced breakdown spectroscopy (LIBS), Ar by quadrupole mass spectrometry (QMS), and ablated mass by laser profilometry. We performed 64 laser ablations on the chondrites to measure spots with a range of K 2 O and Ar content and used the data to construct isochrons to determine the chondrite formation age. The KArLE isochron ages on Pułtusk and Hvittis are 5059 ± 892 Ma and 4721 ± 793 Ma, respectively, which is within the uncertainty of published reference ages, and interpreted as the age of their formation. The uncertainty (2σ) on the KArLE ages obtained in this study is better than 20% (18% for Pułtusk and 17% for Hvittis). The precision, which compares our obtained ages to the reference ages, is also better than 20% (11% for Pułtusk and 4% for Hvittis). These results are encouraging for understanding the limits of this technique to measure ancient planetary samples and for guiding future improvements to the instrument.

Fanny Cattani↗

Charge Transfer Between Ground-State Si(3+) and He at Electron-Volt Energies

The charge-transfer rate coefficient for the reaction Si(3+)(3s(sup 2)S) + He yields products is measured by means of a combined technique of laser ablation and ion storage. A cylindrical radio-frequency ion trap was used to store Si(3+) ions produced by laser ablation of solid silicon targets. The rate coefficient of the reaction was derived from the decay rate of the ion signal. The measured rate coefficient is 6.27(exp +0.68)(sub -0.52) x 10(exp -10)cu cm/s at T(sub equiv) = 3.9 x 10(exp 3)K. This value is about 30% higher than the Landau-Zener calculation of Butler and Dalgarno and is larger by about a factor of 3 than the recent full quantal calculation of Honvault et al.

Fang, Z.↗

Diffusivities of Redox-Sensitive Elements in Basalt vs. Oxygen Fugacity Determined by LA-ICP-MS

Several diffusion experiments were conducted in a piston cylinder device across a range of oxygen fugacities (FMQ-3 FMQ-1.2, FMQ+6) at 1 GPa and 1300 C. This was done to explore the effects of oxygen fugacity (fO2) on diffusivity of redox sensitive trace elements. This allows investigation of how these elements diffuse across the fO2 range encountered in different reservoirs on planets and moons in our solar system. The University of Rochester LA-ICP-MS system was used for analysis of samples. Analyses were conducted using an Agilent 7900 quadrupole mass spectrometer connected to a Photon Machines 193 nm G2 laser ablation (LA) system equipped with a HelEx 2-volume sample chamber. Spots used were 35 micrometers circles spaced at 65 micrometers intervals. Laser fluence was 7.81 J/cm^2 with a rep rate of 10 Hz. The iolite software package was used to reduce data collected from laser ablation analysis of experiments with Si-29 used as the internal standard isotope. Iolite's global fit module was used to simultaneously fit elements' diffusivities in each experiment while keeping the Matano interface constant. Elements analysed include V, Nb, W, Mo, La, Ce, Pr, Sm, Eu, Gd, Ta, and W. Figures

Szumila, Ian↗

Photoresponse of YBa2Cu3O(7-delta) granular and epitaxial superconducting thin films

The response is reported of thin films of YBa2Cu3O(7-delta) with either a very grainy or a smooth epitaxial morphology to visible radiation. SrTiO3 substrates were employed for both types of films. The grainy films were formed by sequential multi-layer electron beam evaporation while the epitaxial films were formed by laser ablation. Both films were patterned into H shaped detectors via a negative photolithographic process employing a Br/ethanol etchant. The bridge region of the H was 50 microns wide. The patterned films formed by laser ablation and sequential evaporation had critical temperatures of 74 K and 72 K respectively. The bridge was current biased and illuminated with chopped He-Ne laser radiation and the voltage developed in response to the illumination was measured. A signal was detected only above the critical temperature and the peak of the response coincided with the resistive transition for both types of films although the correspondence was less exact for the grainy film. The details of the responses and their analysis are presented.

Valco, G. J.↗

Photoresponse of YBa2Cu3O(7-delta) granular and epitaxial superconducting thin films

The response is reported of thin films of YBa2Cu3O(7-delta) with either a very grainy or a smooth epitaxial morphology to visible radiation. SrTiO3 substrates were employed for both types of films. The grainy films were formed by sequential multi-layer electron beam evaporation while the epitaxial films were formed by laser ablation. Both films were patterned into H shaped detectors via a negative photolithographic process employing a Br/ethanol etchant. The bridge region of the H was 50 microns wide. The patterned films formed by laser ablation and sequential evaporation had critical temperatures of 74 K and 72 K respectively. The bridge was current biased and illuminated with chopped He-Ne laser radiation and the voltage developed in response to the illumination was measured. A signal was detected only above the critical temperature and the peak of the response coincided with the resistive transition for both types of films although the correspondence was less exact for the grainy film. The details of the responses and their analysis are presented.

Valco, G. J.↗

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.↗

Diamondlike carbon films as protective coatings for superconducting YBa2Cu3O7 films

We have investigated the use of diamondlike carbon (DLC) films for protecting superconducting YBCO films against degradation from exposure to moisture and acid. YBCO thin films on single crystal LaAlO3 and MgO substrates were deposited by laser ablation followed by DLC encapsulation. DLC films were deposited at pressures ranging from high vacuum to 0.1 Torr He. Substrate temperature was varied from 20 to 100 C during the deposition of DLC. The process compatibility of laser ablation was found convenient to sequentially deposit YBCO and DLC films from high purity stoichiometric targets. Epitaxial YBCO films on (100)LaAlO3 and (100)MgO substrates showed identical superconducting transitions before and after encapsulation by a DLC layer. The encapsulated films showed no degradation due to acid treatment or aging over a period of 45 days.

Ganapathi, L.↗

Application of High-Spatial Resolution LA-MC-ICP-MS in Planetary Materials

High-precision stable and radiogenic isotopic measurements of planetary materials can help elucidate processes taking place during early Solar System formation, as well as during subsequent planetary differentiation. Laser Ablation Multi Collector Inductively Coupled Plasma Mass Spectrometry (LA-MC-ICP-MS) adds the valuable ability of preserving the spatial context of these isotopic measurements, by sampling small sample volumes (~10 – 60 um diameter) using a pulsed laser system. In the Center for Isotope Cosmochemistry and Geochronology (CICG) at NASA Johnson Space Center, these in-situ isotopic measurements are primarily made using the Applied SpectraTM iX-fs-Tandem LA-LIBS Instrument coupled to the Nu InstrumentsTM SP1700 MC-ICP-MS. The instrumental set-up also provides simultaneous Laser Induced Breakdown Spectroscopy (LIBS) measurements and the potential use of a low energy path with a collision/reaction cell for additional interference removal, though we focus here on the typical high-energy LA-MC-ICP-MS operation. We will provide examples of stable (e.g., Mg) and radiogenic (e.g., Lu-Hf) isotopic systems measured in planetary materials and their terrestrial analogs. The measurement of mass dependent Mg isotopic variations is an important tool for reconstructing processes such as evaporation and condensation of solids in the solar nebula. For early Solar System samples, Mg isotope measurements are also important for the short-lived (t1/2 = 0.7 Ma) Al-Mg chronometer. During laser ablation analyses, the measurement of the Al-Mg isotopic system is made in medium mass resolution (RP ~9500 at ~20% transmission) to limit interferences from 48Ti2+ and 48Ca2+ on 24Mg+, in addition to 52Cr2+ and 12C14N+ on 26Mg+. Measured in the mineral zircon, the 176Lu-176Hf decay system is often used for understanding the growth of continents on Earth, and is also a vital aid in deciphering early large-scale planetary differentiation processes, such as the crystallization of the lunar magma ocean, which is thought to be responsible for much of the Moon’s crust. Lu-Hf measurements are made in low resolution mode (RP <2000), with 10 ion masses (from 171Yb to 180Hf) measured simultaneously to facilitate corrections for isobaric interferences from 176Yb and 176Lu on 176Hf.

Jacob B Setera↗

Optimizing a Laser Process for Making Carbon Nanotubes

A systematic experimental study has been performed to determine the effects of each of the operating conditions in a double-pulse laser ablation process that is used to produce single-wall carbon nanotubes (SWCNTs). The comprehensive data compiled in this study have been analyzed to recommend conditions for optimizing the process and scaling up the process for mass production. The double-pulse laser ablation process for making SWCNTs was developed by Rice University researchers. Of all currently known nanotube-synthesizing processes (arc and chemical vapor deposition), this process yields the greatest proportion of SWCNTs in the product material. The aforementioned process conditions are important for optimizing the production of SWCNTs and scaling up production. Reports of previous research (mostly at Rice University) toward optimization of process conditions mention effects of oven temperature and briefly mention effects of flow conditions, but no systematic, comprehensive study of the effects of process conditions was done prior to the study described here. This was a parametric study, in which several production runs were carried out, changing one operating condition for each run. The study involved variation of a total of nine parameters: the sequence of the laser pulses, pulse-separation time, laser pulse energy density, buffer gas (helium or nitrogen instead of argon), oven temperature, pressure, flow speed, inner diameter of the flow tube, and flow-tube material.

Arepalli, Sivaram↗

Patterning of dispenser cathode surfaces to a controlled porosity

A process to pattern slots approximately 1.25 microns in width into 25-micron-thick W films that have been deposited onto flat or concave surfaces is discussed. A 25-micron-thick W film with a high degree of (100) orientation is chemically vapor deposited (CVD) onto a flat or concave Mo mandrel. A 5-micron-thick Al film is deposited onto the CVD W, followed by 2 microns of photoresist. On concave cathodes, XeCl2 laser ablation or X-ray lithography is used to pattern the photoresist, whereas on flat cathodes deep UV lithography can be used. The patterned photoresist serves as the mask in a Cl ion-beam-assisted etching (IBAE) process to pattern the Al. An alternative process is to deposit Al2O3 films onto the W and pattern the Al2O3 using laser ablation. The W film is then patterned to 3-6-micron slot widths using IBAE + ClF3 with the patterned Al or Al2O3 as the mask. Finally, a sputter deposition step is required to close up the slots to approximately 1 micron. The process described is capable of patterning concave dispenser cathodes to a controlled and precise porosity.

Garner, Charles E.↗

Copoly(imide siloxane) Abhesive Materials with Varied Siloxane Oligomer Length

In this work, low surface energy copoly(imide siloxane)s were synthesized with various siloxane segment lengths. Characterization of these materials revealed that domain formation of the low surface energy component within the matrix was more prevalent for longer siloxane segments as indicated by increased opacity, decreased mechanical properties, and variation of the Tg. Incorporation of siloxanes lowered the polymer s surface energy as indicated by water contact angle values. Topographical modification of these materials by laser ablation patterning further reduced the surface energy, even generating superhydrophobic surfaces. Combined, the contact angle data and particle adhesion testing indicated that copoly(imide siloxane) materials may provide greater mitigation to particulate adhesion than polyimide materials alone. These enhanced surface properties for abhesive applications did result in a reduction of the tensile moduli of the copolymers. It is possible that lower siloxane loading levels would result in retention of the mechanical properties of the polyimide while still affording abhesive surface properties. This hypothesis is currently being investigated. Laser ablation patterning offers further reduction in particle retention as the available surface area for particle adhesion is reduced. Pattern variation and size dependencies are currently being evaluated. For the purposes of lunar dust adhesion mitigation, it is likely that this approach, termed passive due to the lack of input from an external energy source, would not be sufficient to mitigate surface contamination or clean contaminated surfaces for some lunar applications. It is feasible to combine these materials with active mitigation strategies - methods that utilize input from external energy sources - would broaden the applicability of such materials for abhesive purposes. Collaborative efforts along these lines have been initiated with researchers at NASA Kennedy Space Center where experiments are being conducted involving a series of embedded electrodes within polymeric matrices.

Wohl, Christoper J.↗

Relationship between LIBS Ablation and Pit Volume for Geologic Samples: Applications for in situ Absolute Geochronology

In planetary sciences, in situ absolute geochronology is a scientific and engineering challenge. Currently, the age of the Martian surface can only be determined by crater density counting. However this method has significant uncertainties and needs to be calibrated with absolute ages. We are developing an instrument to acquire in situ absolute geochronology based on the K‐Ar method. The protocol is based on the laser ablation of a rock by hundreds of laser pulses. Laser Induced Breakdown Spectroscopy (LIBS) gives the potassium content of the ablated material and a mass spectrometer (quadrupole or ion trap) measures the quantity of 40Ar released. In order to accurately measure the quantity of released 40Ar in cases where Ar is an atmospheric constituent (e.g., Mars), the sample is first put into a chamber under high vacuum. The 40Arquantity, the concentration of K and the estimation of the ablated mass are the parameters needed to give the age of the rocks. The main uncertainties with this method are directly linked to the measures of the mass (typically some μg) and of the concentration of K by LIBS (up to 10%). Because the ablated mass is small compared to the mass of the sample, and because material is redeposited onto the sample after ablation, it is not possible to directly measure the ablated mass. Our current protocol measures the ablated volume and estimates the sample density to calculate ablated mass. The precision and accuracy of this method may be improved by using knowledge of the sample's geologic properties to predict its response to laser ablation, i.e., understanding whether natural samples have a predictable relationship between laser energy deposited and resultant ablation volume. In contrast to most previous studies of laser ablation, theoretical equations are not highly applicable. The reasons are numerous, but the most important are: a) geologic rocks are complex, polymineralic materials; b) the conditions of ablation are unusual (for example, variable vacuum pressure), and c) the ablation is made with hundreds of successive laser pulses. In this work, we aim to understand the effects that occur on LIBS spectra when a homogeneous rock or a mineral is ablated under high vacuum. Understanding these effects is important to define best practices for LIBS measurements and may lead to improved measurement (or possibly prediction) of the ablated volume. We will describe our laboratory approach and first results, and discuss its utility for situ absolute geochronology campaigns.

Devismes, D.↗

Determination of Cross-Sectional Area of Focused Picosecond Gaussian Laser Beam

Measurement of the waist diameter of a focused Gaussian-beam at the 1/e(sup 2) intensity, also referred to as spot size, is key to determining the fluence in laser processing experiments. Spot size measurements are also helpful to calculate the threshold energy and threshold fluence of a given material. This work reports an application of a conventional method, by analyzing single laser ablated spots for different laser pulse energies, to determine the cross-sectional area of a focused Gaussian-beam, which has a nominal pulse width of approx. 10 ps. Polished tungsten was used as the target material, due to its low surface roughness and low ablation threshold, to measure the beam waist diameter. From the ablative spot measurements, the ablation threshold fluence of the tungsten substrate was also calculated.

Ledesma, Rodolfo↗

Additional Trials & Tribulations in Synthesizing a Sulfide Standard

Well-characterized sulfide reference materials that can serve as matrix-matched calibrants for in-situ trace element analyses via laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remain elusive. Here, we describe the creation an in-house sulfide standard at NASA JSC that will be used to measure siderophile and chalcophile trace elements in low pressure experimental products, specifically pentlandite ([FeNi]9S8) and pyrrhotite ([FeNi]1-xS), as well as natural sulfides in terrestrial and meteoritic mineral assemblages. Recent methods in creating a homogenous sulfide standard include pressed pellets, synthesized chips, or fused glass [e.g. 1-3]. Other studies, however, have had success in forming homogenous FeS standards via synthesization methods [e.g. 4-6]. We present a variation of the method described in [4], in which we create a pyrrhotite standard doped with a variety of trace elements (Zn, As, Se, Mo, Ru, Rh, Pd, Sn, Sb, Te, W, Os, Ir, Pt, Au) at ~10-40 ppm and Cu at ~200 ppm. Sulfide compositions were constructed using Fe and Ni metal and elemental sulfur powders. Trace elements were added to elemental sulfur from Atomic Absorption Spectroscopy (AAS) elemental standards as either nitrate or chloride solutions to prevent oxidation of the metal powders. The dried sulfur mixture was mixed with Fe and Ni powders and mechanically mixed before two aliquots were placed in separate SiO2 tubes. Each tube was held under vacuum for ~30 minutes, sealed under vacuum, and then heated at 800C for 48 hours. Like [4], the synthesis products were composed of pourous sulfide crystals. Major element analyses of both experimental aliquots, collected using an Electron Probe Microanalyser (EPMA), yield indistinguishable major element compositions (uncertainties in 2SE & 2RSE[%]), with an average of 57.90  0.09 (0.16 %), 4.95  0.03 (0.55 %), and 39.70  0.14 (0.34 %), for Fe, Ni, and S, respectively. Trace element data were measured using a Photon Machines 193nm laser ablation system coupled to a Thermo-Scientific Element-XR ICP-MS. Spot sizes were limited to 50 μm due to the porous nature of the sulfide target material. Trace element abundances, normalized to Fe as an internal standard, were also found to be homogenous between the two aliquots, with weighted mean 2RSE (%) values of <3.0 for all trace elements. Synthesized products were re-powdered and absolute concentrations measured via solution ICP-MS. Although the sulfide appears to be homogenous, sintering experiments will be performed to more closely match the standard density to natural sulfides and minimize differences in ablation behavior. Improved density also allows for higher sensitivity (i.e. more compact target material) and larger spot sizes or traverses, as void space is eliminated. Additional major and trace element analyses on the products of the sintering experiments will be undertaken.

Jacob B Setera↗

Optimization of Picosecond Laser Parameters for Surface Treatment of Composites Using a Design of Experiments (DOE) Approach

Based on guidelines from the Federal Aviation Administration, research supported by the NASA Advanced Composites Project is investigating methods to improve process control for surface preparation and pre-bond surface characterization on aerospace composite structures. The overall goal is to identify high fidelity, rapid, and reproducible surface treatments and surface characterization methods to reduce the uncertainty associated with the bonding process. The desired outcome is a more reliable bonded airframe structure, and to reduce time to achieve certification. In this work, a design of experiments (DoE) approach was conducted to determine optimum laser ablation conditions using a pulsed laser source with a nominal pulse width of 10 picoseconds. The laser power, frequency, scan speed, and number of passes (1 or 2) were varied within the laser system operating boundaries. Aerospace structural carbon fiber reinforced composites (Torayca® 3900-2/T800H) were laser treated, then characterized for contamination, and finally bonded for mechanical testing. Pre-bond characterization included water contact angle (WCA) using a handheld device, ablation depth measurement using scanning electron microscopy (SEM), and silicone contamination measurement using laser induced breakdown spectroscopy (LIBS). In order to accommodate the large number of specimens in the DoE, a rapid-screening, double cantilever beam (DCB) test specimen configuration was devised based on modifications to ASTM D5528. Specimens were tested to assess the failure modes observed under the various laser surface treatment parameters. The models obtained from this DoE indicated that results were most sensitive to variation in the average laser power. Excellent bond performance was observed with nearly 100% cohesive failure for a wide range of laser parameters. Below about 200 mW, adhesive failure was observed because contamination was left on the surface. For laser powers greater than about 600 mW, large amounts of fiber were exposed, and the failure mode was predominately fiber tear.

Palmieri, Frank L.↗