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

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Dereplicating and spatial mapping of secondary metabolites from fungal cultures in situ

Ambient ionization techniques coupled to mass spectrometry have recently become prevalent in natural product research due to their ability to examine secondary metabolites in situ. Identifying, mapping, and monitoring secondary metabolites directly on an organism provides invaluable spatial and temporal details that are lost through traditional extraction processes. Most ambient ionization techniques do not collect mutually supportive data, such as chromatographic retention times and/or UV/VIS spectra, and this can limit the ability to identify certain metabolites, such as differentiating isomers. To overcome this, the droplet liquid microjunction surface sampling probe (droplet LMJ SSP) was coupled with UPLC PDA HRMS MS/MS, thus providing separation, retention times, and UV/VIS data used in traditional dereplication protocols. By capturing these mutually supportive data, the identity of secondary metabolites could be confidently and rapidly assigned in situ. Using the droplet LMJ SSP, a protocol was constructed to analyze the secondary metabolite profile of fungal cultures directly without any sample preparation. The results demonstrate that fungal cultures can be dereplicated from the Petri dish, thus identifying secondary metabolites, including isomers, and confirming them against reference standards. As a result, heat maps, similar to mass spectrometry imaging, can be used to ascertain the location and relative concentration of secondary metabolites directly on the surface and/or surroundings of a fungal culture.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

An Automated Ultraclean Ion Exchange Separation Method for the Determinations of 232Th and 238U in Copper using Inductively Coupled Plasma Mass Spectrometry

This work presents a novel automated analytical method developed for high throughput ultrasensitive determinations of Th and U in copper using inductively coupled plasma mass spectrometry (ICP-MS). The method is based on the use of ultra clean sample preparation procedures including the use of a fully automated off-line chromatography system for the extraction and pre-concentration of the analytes prior to ICP-MS analysis. The separation system is equipped with a single reusable chromatographic column that, with the rigorously clean procedures developed herein, provided a low carryover, low background, and reproducible automated separation method. Isotope dilution methods were used for quantitation. Method Detection Limits (MDLs) of 3.7 and 9.4 fg·g-1 were obtained for the quantitation of 232Th and 238U in copper, respectively, corresponding to activities of 0.0148 and 0.116 microBq·kg-1 for 232Th and 238U, respectively. The analytical method provided high and reproducible tracer recoveries. The use of an automated system significantly reduced the extremely tedious active work time required for the chemist (by ca. 80%) relative to manually performing the separation. This method could be adapted to other critical sample matrices requiring the utmost in high throughput clean chemistry procedures for automated ultrasensitive analyses.

Arnquist, Isaac J.↗
DOE OSTI2016

A Comparative Study of Single-pulse and Double-pulse Laser-Induced Breakdown Spectroscopy with Uranium-containing Samples

Laser-induced breakdown spectroscopy (LIBS) holds potential advantages in special nuclear material (SNM) sensing and nuclear forensics which require rapid analysis, minimal sample preparation and stand-off distance capability. SNM, such as U, however, result in crowded emission spectra with LIBS, and characteristic emission lines are challenging to discern. It is well-known that double-pulse LIBS (DPLIBS) improves the signal intensity for analytes over conventional single-pulse LIBS (SPLIBS). This study investigates U signal in a glass matrix using DPLIBS and compares to signal features obtained using SPLIBS. DPLIBS involves sequential firing of 1.06 µm Nd:YAG pre-pulse and 10.6 µm TEA CO2 heating pulse in near collinear geometry. Optimization of experimental parameters including inter-pulse delay and energy follows identification of characteristic lines and signals for bulk analyte Ca and minor constituent analyte U for both DPLIBS and SPLIBS. Spatial and temporal coupling of the two pulses in the proposed DPLIBS technique yields improvements in analytical merits with negligible further damage to the sample compared to SPLIBS. Subsequently, the study discusses optimum plasma emission conditions of U lines and relative figures of merit in both SPLIBS and DPLIBS. Investigation into plasma characteristics also addresses plausible mechanisms related to observed U analyte signal variation between SPLIBS and DPLIBS.

Skrodzki, P. J.↗
DOE OSTI2014

Towards bio-silicon interfaces: Formation of an ultra-thin self-hydrated artificial membrane composed of dipalmitoylphosphatidylcholine (DPPC) and chitosan deposited in high vacuum from the gas-phase

The recent combination of nanoscale developments with biological molecules for biotechnological research has opened a wide field related to the area of biosensors. In the last years, device manufacturing for medical applications adapted the so-called bottom-up approach, from nanostructures to larger devices. Preparation and characterization of artificial biological membranes is a necessary step for the formation of nano-devices or sensors. In this paper, we describe the formation and characterization of a phospholipid bilayer (dipalmitoylphosphatidylcholine, DPPC) on a mattress of a polysaccharide (Chitosan) that keeps the membrane hydrated. The deposition of Chitosan (∼25 Å) and DPPC (∼60 Å) was performed from the gas phase in high vacuum onto a substrate of Si(100) covered with its native oxide layer. The layer thickness was controlled in situ using Very High Resolution Ellipsometry (VHRE). Raman spectroscopy studies show that neither Chitosan nor DPPC molecules decompose during evaporation. With VHRE and Atomic Force Microscopy we have been able to detect phase transitions in the membrane. The presence of the Chitosan interlayer as a water reservoir is essential for both DPPC bilayer formation and stability, favoring the appearance of phase transitions. Our experiments show that the proposed sample preparation from the gas phase is reproducible and provides a natural environment for the DPPC bilayer. In future work, different Chitosan thicknesses should be studied to achieve a complete and homogeneous interlayer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Rapid paper spray mass spectrometry characterization of uranium and exemplar molecular species

The ability to detect and quantify the presence of specific inorganic elements and complexes is essential for environmental monitoring and nuclear safeguards applications. In this work, paper spray ionization mass spectrometry (PSI–MS) was used for the rapid chemical and isotopic characterization of trace inorganic species collected on cotton swipe substrates. Here, the direct analysis of cotton swipes using this ambient ionization technique led to fast sample analysis that retained original chemical information of the source material with minimal sample preparation. Mass spectra were collected on an atmospheric pressure ionization, high–resolution mass spectrometer for solutions containing uranyl acetate, uranyl chloride, uranyl nitrate, and uranyl tri– n –butylphosphate (uranyl–TBP) complexes. Gadolinium nitrate was used as an internal standard for the quantitative analysis of uranium. To demonstrate the ability to characterize inorganic contaminants in the presence of uranium, a multi–element inorganic standard containing U, Bi, Pb, Cd, Fe, and Zn was deposited onto cotton substrates and directly analyzed without purification. All elements doped on the cotton substrate were detected with strong signal–to–noise (S/N) ratios (S/N~1000 for UO 2 + on multi–element doped swipes) and high integrated intensities (>10 5 counts) from collection periods of approximately 1 min. Limits of detection were determined to be approximately 94 ng for UO 2 + and uranyl acetate through the measurement of ppb level solutions. The rapid analysis of uranium and other inorganic–containing samples while still retaining original chemical information (e.g. uranyl complexation) was demonstrated. Qualitative detection and speciation were achieved in less than 1 min of analysis. For uranium isotopic quantitation, longer accumulations (>15 min) can be sustained to improve the accuracy of minor 235 U isotopic abundance measurements to approximately 1% error.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
NASA NTRS1999

A Mossbauer investigation of iron-rich terrestrial hydrothermal vent systems: lessons for Mars exploration

Hydrothermal spring systems may well have been present on early Mars and could have served as a habitat for primitive life. The integrated instrument suite of the Athena Rover has, as a component on the robotic arm, a Mossbauer spectrometer. In the context of future Mars exploration we present results of Mossbauer analysis of a suite of samples from an iron-rich thermal spring in the Chocolate Pots area of Yellowstone National Park (YNP) and from Obsidian Pool (YNP) and Manitou Springs, Colorado. We have found that Mossbauer spectroscopy can discriminate among the iron-bearing minerals in our samples. Those near the vent and on the surface are identified as ferrihydrite, an amorphous ferric mineraloid. Subsurface samples, collected from cores, which are likely to have undergone inorganic and/or biologically mediated alteration (diagenesis), exhibit spectral signatures that include nontronite (a smectite clay), hematite (alpha-Fe2O3), small-particle/nanophase goethite (alpha-FeOOH), and siderite (FeCO3). We find for iron minerals that Mossbauer spectroscopy is at least as efficient in identification as X-ray diffraction. This observation is important from an exploration standpoint. As a planetary surface instrument, Mossbauer spectroscopy can yield high-quality spectral data without sample preparation (backscatter mode). We have also used field emission scanning electron microscopy (FESEM), in conjunction with energy-dispersive X ray (EDX) fluorescence spectroscopy, to characterize the microbiological component of surface sinters and the relation between the microbiological and the mineralogical framework. Evidence is presented that the minerals found in these deposits can have multi-billion-year residence times and thus may have survived their possible production in a putative early Martian hot spring up to the present day. Examples include the nanophase property and the Mossbauer signature for siderite, which has been identified in a 2.09-billion-year old hematite-rich chert stromatolite. Our research demonstrates that in situ Mossbauer spectroscopy can help determine whether hydrothermal mineral deposits exist on Mars, which is significant for exobiology because of the issue of whether that world ever had conditions conductive to the origin of life. As a useful tool for selection of samples suitable for transport to Earth, Mossbauer spectroscopy will not only serve geological interests but will also have potential for exopaleontology.

NASA Discipline Exobiology↗
DOE OSTI2020

Distinguishing Mesoscale Polar Order (Unidirectional vs Bidirectional) of Cellulose Microfibrils in Plant Cell Walls Using Sum Frequency Generation Spectroscopy

Cellulose in plant cell walls are synthesized as crystalline microfibrils with diameters of 3–4 nm and lengths of around 1–10 μm. These microfibrils are known to be the backbone of cell walls, and their multiscale three-dimensional organization plays a critical role in cell wall functions including plant growth and recalcitrance to degradation. The mesoscale organization of microfibrils over a 1–100 nm range in cell walls is challenging to resolve because most characterization techniques investigating this length scale suffer from low spatial resolution, sample preparation artifacts, or inaccessibility of specific cell types. Here, we report a sum frequency generation (SFG) study determining the mesoscale polarity of cellulose microfibrils in intact plant cell walls. SFG is a nonlinear optical spectroscopy technique sensitive to the molecular-to-mesoscale order of noncentrosymmetric domains in amorphous matrices. However, the quantitative theoretical model to unravel the effect of polarity in packing of noncentrosymmetric domains on SFG spectral features has remained unresolved. In this work, we show how the phase synchronization principle of the SFG process is used to predict the relative intensities of vibrational modes with different polar angles from the noncentrosymmetric domain axis. Applying this model calculation for the first time and employing SFG microscopy, we found that cellulose microfibrils in certain xylem cell walls are deposited unidirectionally (or biased in one direction) instead of the bidirectional polarity which was believed to be dominant in plant cell walls from volume-averaged characterizations of macroscopic samples. Here, with this advancement in SFG analysis, one can now determine the relative polarity of noncentrosymmetric domains such as crystalline biopolymers interspersed in amorphous polymer matrices, which will open opportunities to study new questions that have not been conceived in the past.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Functionalized Polymer Thin Films for Plutonium Capture and Isotopic Screening from Aqueous Sources

The rapid screening of plutonium from aqueous sources remains a critical challenge for nuclear nonproliferation efforts. The determination of trace-level Pu isotopes in water requires offsite sample preparation and analysis; therefore, new methods that combine plutonium purification, concentration, and isotopic screening in a fieldable detection system will provide an invaluable tool for nuclear safeguards. This contribution describes the development and characterization of thin polymer-ligand films for the isolation and concentration of waterborne Pu for direct spectroscopic analyses. Submicron thin films were prepared through spin coating onto Si wafers and consisted of combinations of polystyrene (PS) with dibenzoylmethane, thenoyltrifluoroacetone, and di(2-ethylhexyl)phosphoric acid (HDEHP). Pu uptake studies from solutions at pH from 2.3 to 6.3 indicated that only films containing HDEHP exhibited significant recovery of Pu. High alpha spectroscopy peak energy resolutions were achieved for PS-HDEHP films over a range of film thicknesses from 30 to 250 nm. Furthermore, a separate study was performed to evaluate uptake from a primarily Pu(V) solution where it was observed that doubling the HDEHP loading in the film increased uptake of Pu by an order of magnitude. X-ray photoelectron spectroscopy (XPS) analysis revealed that HDEHP was highly concentrated within the first few nanometers of the film at the higher loading. XPS analysis also revealed that, in the presence of water, HDEHP was stripped from the surface layer of the film at circumneutral pH. While significant losses of ligand were seen in all samples, higher loadings of HDEHP resulted in measurable amounts of ligand retained after a 12-h soak in water. Findings of this study are being used to guide the development of thin-film composite membrane-based detection methods for the rapid, fieldable analysis of Pu in water.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Structure refinement and dielectric relaxation of M-type Ba, Sr, Ba-Sr, and Ba-Pb hexaferrites

M-type hexaferrites with compositions BaFe{sub 12}O{sub 19} (BFO), SrFe{sub 12}O{sub 19} (SFO), Ba{sub 0.5}Sr{sub 0.5}Fe{sub 12}O{sub 19} (BSFO), and Ba{sub 0.5}Pb{sub 0.5}Fe{sub 12}O{sub 19} (BPFO) were synthesized by commercial solid state reaction method. The Rietveld refinement of x-ray powder diffraction revealed a single hexagonal phase with space group P6{sub 3}/mmc for BFO, SFO, and BSFO samples, whereas BPFO sample contains hematite ({alpha}-Fe{sub 2}O{sub 3}) phase with space group R3c along with the M-type main phase. All the samples show dispersion in dielectric constant ({epsilon} Prime ) and dielectric loss (tan {delta}) values with frequency. The values of {epsilon} Prime and tan {delta} increase with increase in temperature due to increase in the number of charge carriers and their mobilities, which are thermally activated. The reciprocal temperature dependence of conductivity ({sigma}{sub ac}) and the most probable relaxation time ({tau}{sub M Double-Prime }) satisfies the Arrhenius relation. A perfect overlapping of the normalized plots of modulus isotherms on a single 'super curve' for all the studied temperatures reveals a temperature independence of dynamic processes involved in conduction and for relaxation. Further, the complex plots of M{sup *} (M Double-Prime vs M Prime ) indicate that dc conductivity dominates in the region below the M Double-Prime {sub max} point. Above M Double-Prime {sub max}, the variations follow Jonscher power law ({sigma} = A{omega}{sup s}) implying that ac conductivity is dominating in this region. Among the prepared samples, SFO hexaferrite has lowest values of {sigma}{sub ac}, {epsilon} Prime , and tan {delta} making it suitable for use in microwave devices.

36 MATERIALS SCIENCE↗
DOE OSTI2015

The Stoichiometry of Synthetic Alunite as a Function of Hydrothermal Aging Investigated by Solid-State NMR Spectroscopy, Powder X-ray Diffraction and Infrared Spectroscopy

The stoichiometry of a series of synthetic alunite [nominally KAl3(SO4)2(OH)6] samples prepared by hydrothermal methods as a function of reaction time (1–31 days) has been investigated by powder X-ray diffraction, Fourier transform infrared spectroscopy as well as solid-state 1H and 27Al magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The 1H MAS NMR spectra recorded at high magnetic field (21.1 T, 900 MHz) allowed for a clear separation of the different proton environments and for quantitative determination of the aluminum vacancy concentration as a function of time. The concentration of structural defects determined from, i.e., aluminum vacancies was reduced from 4 to 1 %, as the reaction time was extended from one to 31 days based on 1H MAS NMR. This was further supported by an increase of the unit cell parameter c, which is indicative of the relative concentration of potassium defects present, from 17.261(1) to 17.324(5) Å. Solid-state 27Al MAS NMR revealed a decrease in the defect concentration as a function of time and showed the presence of 7–10 % impurities in the samples.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2012

Synthesis dependent characteristics of Sr{sub 1-x}Mn{sub x}TiO{sub 3} (x=0.03, 0.05, 0.07 and 0.09)

Sr{sub 1-x}Mn{sub x}TiO{sub 3} (where x=0.03, 0.05, 0.07 and 0.09) was synthesized via different routes that include solid-state, oxalate precipitation and freeze drying. In oxalate precipitation technique, compositions corresponding to 3 and 5 mol% doping of Mn were monophasic whereas the higher compositions revealed the presence of the secondary phases such as MnO, Mn{sub 3}O{sub 4} etc., as confirmed by high resolution X-ray diffraction (XRD) studies. The decomposition behavior of the precursors prepared using oxalate precipitation method corresponding to the above mentioned compositions was studied. Nanopowders of compositions pertaining to 5 to 9 mol% of Mn doping were obtained using freeze-drying technique. The average crystallite size of these nanopowders was found to be in the 35 to 65 nm range. The microstructural studies carried out on the sintered ceramics, fabricated using powders synthesized by different routes established the fine grained nature (<1 {mu}m) of the one obtained by freeze drying method. Raman scattering studies were carried out in order to complement the observations made from XRD regarding the phase purity. The dielectric properties of the ceramics obtained by different synthesis routes were studied in the 80-300 K temperature range at 100 kHz and the effect of grain size has been discussed. - Graphical abstract: XRD patterns of Sr{sub 1-x}Mn{sub x}TiO{sub 3} (x=0.03 and 0.05) obtained by oxalate precipitation technique along with that of the nanopowders for x=0.05, 0.07 and 0.09 obtained by freeze drying method, microstructural characterization and synthesis dependent dielectric behavior. Highlights: Black-Right-Pointing-Pointer Monophasic samples obtained for compositions Sr{sub 1-x}Mn{sub x}TiO{sub 3} with x=0.03 and 0.05. Black-Right-Pointing-Pointer Nanopowders of Sr{sub 1-x}Mn{sub x}TiO{sub 3} with x=0.05, 0.07 and 0.09 were synthesized by freeze-drying method. Black-Right-Pointing-Pointer Phase purity of samples synthesized using freeze drying method were studied at different sintering temperatures. Black-Right-Pointing-Pointer Analysis of Raman spectra for samples prepared by both oxalate precipitation and freeze-drying. Black-Right-Pointing-Pointer Microstructure dependent dielectric characteristics have been illustrated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

High-Temperature Grafting Silylation for Minimizing Leaching of Acid Functionality from Hydrophobic Mesoporous Silicas Used as Catalysts in the Liquid Phase

Ordered-hexagonal silica materials, such as Mobil crystalline material-41 and Santa Barbara amorphous-15, have important applications in heterogeneous catalysis and biomass conversion due to their chemical stability and mesoporous structure. Low-temperature grafting (LG) is one of the most common functionalization methods used to modify the acidity/basicity or hydrophobicity/hydrophilicity of the surface. However, the materials prepared by this method are prone to leaching of functional groups into the reaction medium. The exact nature of the leaching phenomenon has not been fully addressed in the literature. In this contribution, we have investigated this process at the molecular level by combining well-controlled reaction experiments and several characterization techniques (Fourier transform infrared, 1 H– 29 Si cross-polarization magic-angle spinning NMR, X-ray diffraction, thermogravimetric analysis, and N 2 adsorption–desorption). We have found that leaching is originated by the presence of terminal surface silanols, which render the catalysts susceptible to the attack of water and polar compounds. Hence, instead of simple detaching of functional groups, leaching can be better described as a partial dissolution of the surface layers of the silica, which of course also removes the functional groups during this process. Therefore, an effective strategy to minimize leaching is to reduce the density of free silanols via full functionalization of the surface. Here, we propose a novel silylation method, high-temperature grafting, which allows the grafting process to be conducted at high temperatures (180 °C) under solvent-free conditions. By this method, a more complete silylation of surface silanols can be obtained. Consequently, the samples prepared by this high-temperature grafting method show to be highly stable during acid-catalyzed alkylation reaction, conducted under severe conditions (high temperature and in the presence of polar solvents).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

NanoSIMS for biological applications: Current practices and analyses

Secondary ion mass spectrometry (SIMS) has become an increasingly utilized tool in biologically relevant studies. Of these, high lateral resolution methodologies using the NanoSIMS 50/50L have been especially powerful within many biological fields over the past decade. Here, the authors provide a review of this technology, sample preparation and analysis considerations, examples of recent biological studies, data analyses, and current outlooks. Specifically, the authors offer an overview of SIMS and development of the NanoSIMS. The authors describe the major experimental factors that should be considered prior to NanoSIMS analysis and then provide information on best practices for data analysis and image generation, which includes an in-depth discussion of appropriate colormaps. Additionally, the authors provide an open-source method for data representation that allows simultaneous visualization of secondary electron and ion information within a single image. Finally, the authors present a perspective on the future of this technology and where they think it will have the greatest impact in near future.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2015

Study of Mössbauer and magnetic properties of Al{sup 3+} ions doped superparamagnetic nano ferrites

Nanocrystalline Al{sup 3+} ions doped Mg{sub 0.2}Mn{sub 0.5}Ni{sub 0.3}Al{sub y}Fe{sub 2-y}O{sub 4} compositions, where y=0.0 and 0.10 have been synthesized by citrate precursor method. Crystal structure and magnetic properties have been investigated at room temperature by means of X-ray diffraction, TEM, LCR meter, VSM and Mössbauer spectroscopy. Particle size and lattice parameter has been found to decrease as non-magnetic Al content increased. Relative loss factor has very low value in range of 10{sup −6}–10{sup −5} which is three orders of magnitude less than samples prepared by conventional method. The Mössbauer spectroscopy results shows superparamagnetism. The isomer shift corresponding to Fe{sup 3+} ions do not show any significant variation which indicates that replacement of Fe{sup 3+} ions do not affect significantly the d-electrons density which in turn affects the s-electrons density around Fe{sup 3+} nuclei. The nuclear hyperfine magnetic fields have been found to decrease at A-site and B-site with increasing substitution of Al{sup 3+} ions in Mg-Mn-Ni ferrite.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Physical Properties of Mn{sub 2}O{sub 3} Nanoparticles Synthesized by Co-precipitation Method at Different pH Values

Mn{sub 2}O{sub 3} nanoparticles were synthesized at different pH values ranging from 10 to 13 by co-precipitation technique. The characterization of all samples were completed by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR), ultraviolet-absorption spectroscopy (UV), Raman spectroscopy, and M–H loop measurements. The XRD spectra show that the structure of Mn{sub 2}O{sub 3} is cubic, and the lattice parameter a decreases as pH increases. Crystalline size, determined from TEM and XRD analyses, decreases as pH increases. TGA curves show that a mass loss is significantly affected as pH increases, indicating the decomposition of organic species besides the oxidation of Mn{sub 2}O{sub 3} to Mn{sub 3}O{sub 4}. FTIR spectra indicate that the absorption peaks at 593.73 and 519.09 cm{sup − 11} referred to the stretching vibration of Mn–O and Mn–O–Mn bonds during the synthesis of Mn{sub 2}O{sub 3} nanoparticles. UV-visible spectroscopy is measured in the range 250–800 nm and showed a deviation to the lower wavelength in addition to an increase in the band-gap energy (E{sub g}) values from 1.012 to 1.370 eV is obtained. Raman spectra shows a slight deviation to the left which is conversely proportional to the crystalline size. M–H loops for the prepared samples were measured and the results of retentivity (M{sub s}) and coercivity (H{sub c}) were discussed.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
NASA NTRS2005

Mechanical Properties and Microstructure Investigation of Lead Free Solder

While the electronics industry appears to be focusing on Sn-Ag-Cu as the alloy of choice for lead free electronics assembly, ,the exact composition varies by geographic region, supplier and user. Add to that dissolved copper and silver from the printed circuit board traces and surface finish, and there can be significant variation in the final solder joint composition. A systematic study of the mechanical and microstructural properties of Sn-Ag-Cu alloys with Ag varying from 2wt% to 4wt% and Cu varying from 0.5wt% to lSwt%, was undertaken in this research study. Different sample preparation techniques (water quenched, oil quenched and water quenched followed by reflow) were explored and the resulting microstructure compared to that of a typical reflowed lead free chip scale package (CSP) solder joint. Tensile properties (modulus, 0.2% yield strength and the ultimate tensile strength) and creep behavior of selected alloy compositions (Sn-4Ag-1 X u , Sn-4Ag-OSCu, Sn- 2Ag-1 X u , Sn-2Ag-OSCu, Sn-3.5Ag-O.SCu) were determined for three conditions: as- cast; aged for 100 hours at 125OC; and aged for 250 hours at 125OC. There was no significant difference in Young's Modulus as a function of alloy composition. After an initial decrease in modulus after 100 hours at 125"C, there was an insignificant change with further aging. The distribution of 0.2% strain yield stress and ultimate tensile strength as a function of alloy composition was more significant and decreased with aging time and temperature. The microstructures of these alloys were examined using light and scanning electron microscopy (LM and SEM) respectively and SEM based energy dispersive x-ray spectroscopy (EDS). Fracture surface and cross-section analysis were performed on the specimens after creep testing. The creep testing results and the effect of high temperature aging on mechanical properties is presented for the oil quenched samples. In general the microstructure of oil quenched specimen exhibited a eutectic region of Sn with moderately dispersed Ag3Sn intermetallic, surrounded by a dendritic Sn-rich phase. The SEM images of the fracture surface indicated the presence of a tough shear surface at the initial cavity break area and a break line in the middle of specimen along the failure direction. A hyperbolic-sine creep model was adopted and used to fit the creep experiment data. The effect on the mechanical properties by adding the quaternary element bismuth to the Sn-3.5Ag-0.8Cu alloy was measured and compared with the mechanical properties of the ternary alloys. The results of this research study provide necessary data for the modeling of solder joint reliability for a range of Sn-Ag-Cu compositions and a baseline for evaluating the effects of subsequent quaternary additions.

Wang, Qing↗
DOE OSTI2021

Grafted nickel-promoter catalysts for dry reforming of methane identified through high-throughput experimentation

High-throughput synthesis of a series of monometallic and bimetallic catalysts (45 bimetallic and 50 monometallic samples) consisting of nickel and one of nine different metal promoters (B, Co, Cu, Fe, Mg, Mn, Sn, V and Zn) supported on one of six different metal oxides alumina, ceria, magnesia, silica and titania) is carried out via organometallic grafting using a robotic platform. The catalysts are evaluated for their activity and selectivity for the dry reforming of methane at a feed ratio of CH 4 :CO 2 of 1 at 650–800 °C in a parallel flow reactor system. The type of oxide support prevails over the type of additive for both catalyst activity and stability. On Al 2 O 3 and MgO, Fe was found to be the best promoter; on SiO 2 , Cu is the best promoter at 700 °C and higher, while on TiO 2 , Mn is found to enhance the conversion at 800 °C. On CeO 2 , all additives except Fe have beneficial effects. Twenty-five catalysts show > 90% methane conversion with ten catalysts showing > 95% conversion at 800 °C with the H 2 :CO ratios ranging from 0.8 to 1.2. Amongst the ten highest performers, NiFe/Al 2 O 3 and NiFe/MgO are more active than Ni/Al 2 O 3 and Ni/MgO, respectively and were stable over a period of 25 h at 800 °C. Characterization on the as-prepared samples reveals highly dispersed phase, while after reduction in H 2 , highly dispersed and reduced nickel particles up to 10 nm are formed. The particles do not increase in size under dry reforming reaction conditions at 800 °C. An increased hydrogen consumption observed during H 2 -TPR of the nickel particles is positively correlated with methane conversion for Al 2 O 3 -based catalysts. The resistance to deactivation by coking and variation in coke structure are investigated by spectroscopic and microscopic methods to identify the relationship between metal promoters, alloy formation, and type of surface carbon deposits. Carbon whiskers were observed on the ten selected spent samples and are preferentially deposited on Ni rather than on the promoters. Carbon nanotube formation and metal particle removal from support were not observed to cause deactivation while amorphous carbon formation was clearly linked to catalyst deactivation, as amorphous carbon could encapsulate nickel, either on the support or at the end of the carbon nanotube. Furthermore, the organometallic grafting technique is an efficient and suitable technique for synthesizing highly dispersed and homogeneous phases which lead to high conversion and high durability for dry reforming of methane.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Porous Chromatographic Materials as Substrates for Preparing Synthetic Nuclear Explosion Debris Particles

In this study, we investigated several porous chromatographic materials as synthetic substrates for preparing surrogate nuclear explosion debris particles. The resulting synthetic debris materials are of interest for use in developing analytical methods. Eighteen metals, including some of forensic interest, were loaded onto materials by immersing them in metal solutions (556 mg/L of each metal) to fill the pores, applying gentle heat (110°C) to drive off water, and then treating them at high temperatures (up to 800°C) in air to form less soluble metal species. High-boiling-point metals were uniformly loaded on spherical controlled-pore glass to emulate early fallout, whereas low-boiling-point metals were loaded on core-shell silica to represent coated particles formed later in the nuclear fallout-formation process. Analytical studies were applied to characterize solubility, material balance, and formation of recalcitrant species. Dissolution experiments indicated loading was 1.5 to 3 times higher than expected from the pore volume alone, a result attributed to surface coating. Analysis of load solutions before and after filling the material pores revealed that most metals were passively loaded; that is, solutions filled the pores without active metal discrimination. However, niobium and tin concentrations were lower in solutions after pore filling, and were found in elevated concentrations in the final products, indicating some metals were selectively loaded. High-temperature treatments caused reduced solubility of several metal species, and loss of some metals (rhenium and tellurium) because volatile species were formed. Sample preparation reproducibility was high (the inter-batch relative standard deviation was 7.8%, and the intra-batch relative standard deviation was 0.84%) indicating that this material is suitable for use as a working standard for analytical methods development. We anticipate future standardized radionuclide-loaded materials will find use in radioanalytical methods development and/or serve as a starting material for the synthesis of more complex forms of nuclear explosion debris (e.g., Trinitite).

36 MATERIALS SCIENCE↗