Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “SAMPLE PREPARATION”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
DOE OSTI2011

Magnetic spectroscopy and microscopy of functional materials

Heusler intermetallics Mn 2 Y Ga and X 2 MnGa (X; Y =Fe, Co, Ni) undergo tetragonal magnetostructural transitions that can result in half metallicity, magnetic shape memory, or the magnetocaloric effect. Understanding the magnetism and magnetic behavior in functional materials is often the most direct route to being able to optimize current materials for todays applications and to design novel ones for tomorrow. Synchrotron soft x-ray magnetic spectromicroscopy techniques are well suited to explore the the competing effects from the magnetization and the lattice parameters in these materials as they provide detailed element-, valence-, and site-specifc information on the coupling of crystallographic ordering and electronic structure as well as external parameters like temperature and pressure on the bonding and exchange. Fundamental work preparing the model systems of spintronic, multiferroic, and energy-related compositions is presented for context. The methodology of synchrotron spectroscopy is presented and applied to not only magnetic characterization but also of developing a systematic screening method for future examples of materials exhibiting any of the above effects. The chapter progression is as follows: an introduction to the concepts and materials under consideration (Chapter 1); an overview of sample preparation techniques and results, and the kinds of characterization methods employed (Chapter 2); spectro- and microscopic explorations of X 2 MnGa/Ge (Chapter 3); spectroscopic investigations of the composition series Mn 2 Y Ga to the logical Mn 3 Ga endpoint (Chapter 4); and a summary and overview of upcoming work (Chapter 5). Appendices include the results of a Think Tank for the Graduate School of Excellence MAINZ (Appendix A) and details of an imaging project now in progress on magnetic reversal and domain wall observation in the classical Heusler material Co 2 FeSi (Appendix B).

36 MATERIALS SCIENCE↗
DOE OSTI2017

Nominations for the 2017 NNSA Pollution Prevention Awards

In the field of nuclear forensics, one of the biggest challenges is to dissolve postdetonation debris for analysis. Debris generated after a nuclear detonation is a glassy material that is difficult to dissolve with chemicals. Traditionally, concentrated nitric acid, hydrofluoric acid, or sulfuric acid are employed during the dissolution. These acids, due to their corrosive nature, are not suitable for in-field/on-site sample preparations. Uranium oxides are commonly present in nuclear fuel processing plants and nuclear research facilities. In uranium oxides, the level of uranium isotope enrichment is a sensitive indicator for nuclear nonproliferation and is monitored closely by the International Atomic Energy Agency (IAEA) to ensure there is no misuse of nuclear material or technology for nuclear weapons. During an IAEA on-site inspection at a facility, environmental surface swipe samples are collected and transported to the IAEA headquarters or network of analytical laboratories for further processing. Uranium oxide particles collected on the swipe medium are typically dissolved with inorganic acids and are then analyzed for uranium isotopic compositions. To improve the responsiveness of on-site inspections, in-field detection techniques have been recently explored. However, in-field analysis is bottlenecked by time-consuming and hazardous dissolution procedures, as corrosive inorganic acids must be used. Corrosive chemicals are difficult to use in the field due to personnel safety considerations, and the transportation of such chemicals is highly regulated. It was therefore necessary to develop fast uranium oxide dissolution methods using less hazardous chemicals in support of the rapid infield detection of anomalies in declared nuclear processes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Towards a method of rapid extraction of strontium-90 from urine: urine pretreatment and alkali metal removal

A technical program to support the Centers of Disease Control and Prevention is being developed to provide an analytical method for rapid extraction of Sr-90 from urine, with the intent of assessing the general population’s exposure during an emergency response to a radiological terrorist event. Results are presented on the progress in urine sample preparation and chemical separation steps that provide an accurate and quantitative detection of Sr-90 based upon an automated column separation sequence and a liquid scintillation assay. Batch extractions were used to evaluate the urine pretreatment and the column separation efficiency and loading capacity based upon commercial, extractant-loaded resins. An efficient pretreatment process for decolorizing and removing organics from urine without measurable loss of radiostrontium from the sample was demonstrated. In addition, the Diphonix® resin shows promise for the removal of high concentrations of common strontium interferents in urine as a first separation step for Sr-90 analysis.

61 RADIATION PROTECTION AND DOSIMETRY↗
NASA NTRS1997

X-Ray Transmission Microscope Development

We have succeeded in meeting the goals set out in the proposal. A cadre of detector technologies is available to suit the requirements of the experiment. Resolutions of both real-time and absolute limits to resolution exceed the initial aspirations. Obtaining sufficient contrast is still a significant limitation but can be overcome by Judicious selection of the specimen composition. This can only take time and trial and error for a successful result. The 4th generation furnace provides the capability of real-time in-situ observations of composite alloy development. A low detection sensitivity however, has still made it difficult to observe dendritic growth, although it has been 'seen' in raw video; it was not a recordable signal. We have examined flight ampoules with XTM to observe particle and thermocouple placement, crucible flaws and cracks in collaboration with the Particle Pushing and Engulfment flight experiment (Dr. Stefanescu, UA, P.I.). The value of an in flight XTM to guard against experiment failure and safety assurance is obvious. Although not attributable to equipment limitations, a quest to observe particle pushing was not successful. We tried at length to prepare specimens that would demonstrate particle pushing. Instead, we were successful in imaging the interface deformation due to the thermal field distortion of a ceramic particle or void and to compare to calculated shapes. In theory, we should have been able to make major inroads to this field if the particles could be pushed and the velocities adjusted to make critical measurements. On the other hand, critical issues of sample preparation for the PEP flight experiment were established, particularly the clustering of particles and trapped voids. In this regard, the XTM did prove very useful so that flight specimens would work as expected and to perform post flight analysis. Although not a clear result, particle pushing of precipitates was observed in an Al-Si-Mn alloy. It may be that to be pushed, the particles need to be small and have clean surfaces like one might obtain from in-situ precipitation. The ability to image features in real time skill enable more fundamental and detailed understanding of solidification dynamics in microgravity than had previously been possible, thus, allowing the full benefits of microgravity experiments be applied towards rigorous testing of critical solidification models. The XTM is also a valuable tool for post solidification metallography. The 3-dimensional distribution of solute and solidification features within the specimen volume can be viewed without sectioning or other treatment when the solute has sufficiently higher atomic mass than the solvent. Thus the XTM could provide the first practical method for on orbit microstructural (metallographic) analysis by the astronauts or by telescience.

Kaukler, William F.↗
NASA NTRS2003

Quantitating Iron in Serum Ferritin by Use of ICP-MS

A laboratory method has been devised to enable measurement of the concentration of iron bound in ferritin from small samples of blood (serum). Derived partly from a prior method that depends on large samples of blood, this method involves the use of an inductively-coupled-plasma mass spectrometer (ICP-MS). Ferritin is a complex of iron with the protein apoferritin. Heretofore, measurements of the concentration of serum ferritin (as distinguished from direct measurements of the concentration of iron in serum ferritin) have been used to assess iron stores in humans. Low levels of serum ferritin could indicate the first stage of iron depletion. High levels of serum ferritin could indicate high levels of iron (for example, in connection with hereditary hemochromatosis an iron-overload illness that is characterized by progressive organ damage and can be fatal). However, the picture is complicated: A high level of serum ferritin could also indicate stress and/or inflammation instead of (or in addition to) iron overload, and low serum iron concentration could indicate inflammation rather than iron deficiency. Only when concentrations of both serum iron and serum ferritin increase and decrease together can the patient s iron status be assessed accurately. Hence, in enabling accurate measurement of the iron content of serum ferritin, the present method can improve the diagnosis of the patient s iron status. The prior method of measuring the concentration of iron involves the use of an atomic-absorption spectrophotometer with a graphite furnace. The present method incorporates a modified version of the sample- preparation process of the prior method. First, ferritin is isolated; more specifically, it is immobilized by immunoprecipitation with rabbit antihuman polyclonal antibody bound to agarose beads. The ferritin is then separated from other iron-containing proteins and free iron by a series of centrifugation and wash steps. Next, the ferritin is digested with nitric acid to extract its iron content. Finally, a micronebulizer is used to inject the sample of the product of the digestion into the ICPMS for analysis of its iron content. The sensitivity of the ICP-MS is high enough to enable it to characterize samples smaller than those required in the prior method (samples can be 0.15 to 0.60 mL).

Smith, Scott M.↗
DOE OSTI2013

Facile scalable synthesis of Co{sub 3}O{sub 4}/carbon nanotube hybrids as superior anode materials for lithium-ion batteries

Graphical abstract: Co{sub 3}O{sub 4}/MWCNT hybrids were synthesized via strong ultra-sonication assisted shaking processes. The resultant samples as anode electrode display enhanced cycling performance and rate capability compared with pure Co{sub 3}O{sub 4} particle. - Highlights: • Co{sub 3}O{sub 4}/MWCNT hybrids were synthesized via ultra-sonication assisted shaking process. • The resulting Co{sub 3}O{sub 4} nanoparticles are highly dispersed onto MWCNT network backbone. • Co{sub 3}O{sub 4}/MWCNT hybrid displays highly enhanced lithium storage properties. • The present synthetic approach is facile, controllable, and scalable. - Abstract: In this report, Co{sub 3}O{sub 4}/multiple-wall carbon nanotube (MWCNT) hybrid materials were synthesized via strong ultrasonication-assisted shaking and magnetic stirring processes. The prepared samples were well characterized by utilizing powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectroscopy techniques. Results indicated that the resulting Co{sub 3}O{sub 4} nanoparticles were highly dispersed in the MWCNT network backbone and further form Co{sub 3}O{sub 4}/MWCNT hybrid materials. The obtained Co{sub 3}O{sub 4}/MWCNT hybrids can be employed as anode electrode in Lithium-ion batteries and deliver as high as discharge capacity of 1250 mA h g{sup −1} at a current density of 0.2 C, additionally, 81% of the discharge capacity for sample 2 with 20 wt.% MWCNT loading could be retained after 70 cycles, which could be associated with the specific hybrid structure of the electrode as well as the addition of MWCNT. Most importantly, the present synthetic approach is facile, controllable, and scalable, which allowing it more easily adapted to prepare other hybrid materials with specific architectures.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Structural, magnetic and dielectric properties of Bi{sub 1-y}Sr{sub y}Fe{sub (1-y)(1-x)}Sc{sub (1-y)x}Ti{sub y}O{sub 3} (x = 0-0.2, y = 0.1-0.3) ceramics

Graphical abstract: Bi{sub 1-y}Sr{sub y}Fe{sub (1-y)(1-x)}Sc{sub (1-y)x}Ti{sub y}O{sub 3} (x = 0-0.2, y = 0.1-0.3) ceramics were obtained by solid-state reaction method. Addition of scandium could simultaneously reduce magnetic coercive field and enhance dielectric properties of prepared samples. Research highlights: {yields} The electrical resistivity of BiFeO{sub 3} is enhanced by forming solid solution with SrTiO{sub 3}. {yields} We further replace Fe{sup 3+} by Sc{sup 3+} in solid solution to reduce H{sub c} and achieve a soft magnet. {yields} Structure-magnetic property relationship has been established by Rietveld refinement. {yields} Sc{sup 3+} substitution can inhibit the dielectric loss effectively. -- Abstract: In this study, bulk ceramics with general formula Bi{sub 1-y}Sr{sub y}Fe{sub (1-y)(1-x)}Sc{sub (1-y)x}Ti{sub y}O{sub 3} (x = 0-0.2, y = 0.1-0.3 mol%) were prepared by traditional solid-state reaction method. As a comparison, bulk BiFeO{sub 3} (BF) was also sintered by rapid sintering method. Their structural, magnetic, dielectric properties were investigated. X-ray diffraction analysis indicated that apart from a small amount of secondary phase detected in BF, all other samples crystallized in pure perovskite structure and maintained original R3c space group. The room temperature M-H curves were obtained. While BF had a coercive magnetic field (H{sub c}) of 150 Oe, Bi{sub 1-y}Sr{sub y}Fe{sub 1-y}Ti{sub y}O{sub 3} solid solutions had a much larger value (for y = 0.1, 0.2, 0.3, H{sub c} were 4537, 5230 and 3578 Oe, respectively). Sc{sup 3+} substitution decreased the H{sub c} values of these solid solutions remarkably, and resulted in soft magnetic properties, as well as a decrease of the dielectric loss. At 1 MHz, the tan {delta} of Bi{sub 0.7}Sr{sub 0.3}Fe{sub 0.7(1-x)}Sc{sub 0.7x}Ti{sub 0.3}O{sub 3} with x = 0.05, 0.1, 0.15, 0.2 were 0.1545, 0.1078, 0.1046 and 0.1701, respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Methods for Quantitative Thermal Analysis of Lithium Solid-State and Beyond Battery Safety

The use of differential scanning calorimetry (DSC) to measure the thermal behavior of individual components and electrolyte/electrode combinations is common. However, here we focus on DSC tests on an anode, cathode, and electrolyte (ACE) component combination over a temperature range that includes many of the phase transitions and key reactions (i.e., to 500 °C) that contribute to thermal runaway. This method can help quantify the complex reaction network in a full cell, thereby informing potential safety issues. Here, we used DSC heat flow data from a solid-state Li 0.43 CoO 2 +C+PVDF | LLZO | Li metal ACE sample and its components to quantify key factors affecting results. We focused on three areas: (1) ACE sample preparation and assembly in DSC pans, (2) DSC measurement parameters, and (3) heat flow analysis. Key points include the choice of component ratios (e.g., commercially relevant N:P capacity ratio), the importance of conductive carbon and binder, type of pan used, DSC ramp rate, and integration method used when dealing with broad and overlapping exothermic peaks. This work deepens the scientific basis and best practices for obtaining heat flow data from ACE samples for early-stage evaluation of solid-state and beyond battery safety.

25 ENERGY STORAGE↗
DOE OSTI2018

Colloidal Synthesis of Bulk-Bandgap Lead Selenide Nanocrystals

Lead selenide quantum dots (QDs) are low-bandgap IV-VI semiconducting nanomaterials that have been studied for a variety of applications. Their preparation using colloidal methods can create small spherical to larger cubic nanocrystals, with an upper limit of ~17 nm reported to date. Here we describe methods for preparing cubic PbSe nanocrystals over a 20–40 nm size range using a twostep procedure. Specifically, ~10 nm PbSe QDs are generated using the rapid injection method, the products from which are overcoated with additional lead and selenium precursors. The use of two lead reagents were studied; lead oleate resulted in a maximum of 20 nm cubes, while more reactive lead hexyldecanoate resulted in much larger nanomaterials with bulk bandgaps. However, PbSe samples prepared with lead hexyldecanoate also contained agglomerates. Special care must be taken when characterizing larger strained nanomaterials with X-ray powder diffraction, for which the Scherrer equation is inadequate. A more rigorous approach using the Williamson–Hall method provides characterizations that are consistent with electron microscopy analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Radionuclide measurements by accelerator mass spectrometry at Arizona

Over the past years, Tandem Accelerator Mass Spectrometry (TAMS) has become established as an important method for radionuclide analysis. In the Arizona system the accelerator is operated at a thermal voltage of 1.8MV for C-14 analysis, and 1.6 to 2MV for Be-10. Samples are inserted into a cesium sputter ion source in solid form. Negative ions sputtered from the target are accelerated to about 25kV, and the injection magnet selects ions of a particular mass. Ions of the 3+ charge state, having an energy of about 9MeV are selected by an electrostatic deflector, surviving ions pass through two magnets, where only ions of the desired mass-energy product are selected. The final detector is a combination ionization chamber to measure energy loss (and hence, Z), and a silicon surface-barrier detector which measures residual energy. After counting the trace iosotope for a fixed time, the injected ions are switched to the major isotope used for normalization. These ions are deflected into a Faraday cup after the first high-energy magnet. Repeated measurements of the isotope ratio of both sample and standards results in a measurement of the concentration of the radionuclide. Recent improvements in sample preparation for C-14 make preparation of high-beam current graphite targets directly from CO2 feasible. Except for some measurements of standards and backgrounds for Be-10 measurements to date have been on C-14. Although most results have been in archaeology and quaternary geology, studies have been expanded to include cosmogenic C-14 in meteorites. The data obtained so far tend to confirm the antiquity of Antarctic meteorites from the Allan Hills site. Data on three samples of Yamato meteorites gave terrestrial ages of between about 3 and 22 thousand years.

Jull, A. J. T.↗
DOE OSTI2018

Structural and magnetic properties of praseodymium substituted barium-based spinel ferrites

Highlights: • Barium based spinel ferrites were successfully synthesized by Sol-gel method. • The spinel phase has been observed in all samples. • Ac susceptibility of all the samples is presented. • The Ms Decreases with increasing Pr contents while Hc increases. - Abstract: In this research work BaPr{sub x}Fe{sub 2-x}O{sub 4} (x = 0.0, 0.025, 0.05, 0.075, 0.10) spinel ferrites have been synthesized successfully by sol-gel technique. X-ray diffraction analysis confirmed the fcc spinel phase of the synthesized samples. All the samples showed inhomogeneous grain size distribution observed through scanning electron microscopy (SEM).Temperature dependence normalized AC susceptibility and Curie temperature studies revealed that BaFe{sub 2}O{sub 4} exhibited multidomain (MD) structure with high Curie temperature. On the other hand, multidomain to single domain (SD) transitions occurred when the praseodymium is substituted into barium spinel ferrites. Narrow loops showed the soft nature of ferrites and it was confirmed from magnetic properties of the prepared samples. Decreasing trend of saturation magnetization and remanence was observed with the substitution of praseodymium contents. Coercivity and anisotropy constant both enhanced with the praseodymium concentration. The above-mentioned parameters revealed that the synthesized spinel ferrites might be useful for the of high-density magnetic recording applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Construction of hybrid Ag2CO3/AgVO3 nanowires with enhanced visible light photocatalytic activity

Highlights: • Hybrid Ag{sub 2}CO{sub 3}/AgVO{sub 3} nanowires were successfully synthesized. • The as-prepared sample displayed highly enhanced photocatalytic activity. • Possible photocatalytic mechanism for RhB degradation was proposed. - Abstract: Visible light driven pollutant degradation by photocatalyst was one of most efficient and economical strategies for environmental application. The focus and challenge was to fabricate efficient artificial photocatalysts. In this work, hybrid Ag{sub 2}CO{sub 3}/AgVO{sub 3} nanowires were first reported to be successfully synthesized by the facile ion-exchange method. The as-prepared Ag{sub 2}CO{sub 3}/AgVO{sub 3} nanowires showed highly improved visible light photocatalytic activity for RhB degradation, and the optimized Ag{sub 2}CO{sub 3}/AgVO{sub 3}-40% photocatalyst exhibited the best photocatalytic activity, which is 3.6 times of pure Ag{sub 2}CO{sub 3} and 13.3 times of pure AgVO{sub 3} catalysts, mainly due to the formation of Ag nanoparticles and Ag{sub 2}CO{sub 3}/AgVO{sub 3} heterojunction for charge separation. The degradation of RhB solution was mainly attributed to direct hole oxidation, which was also confirmed by the active species trapping experiments. Finally, the possible visible light photocatalytic mechanism of Ag/Ag{sub 2}CO{sub 3}/AgVO{sub 3} composites for RhB degradation was proposed.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

Synthesis, characterization, and gas-sensing properties of monodispersed SnO{sub 2} nanocubes

Monodispersed single-crystalline SnO{sub 2} nanocubes with exposed a large percentage of high-energy surfaces have been synthesized by a simple solvothermal process at low temperature without any templates and catalysts. The as-prepared samples have been characterized by X-ray diffraction and transmission electron microscopy. Many outstanding characters of the final products have been shown, such as uniform particle size, high purity, and monodispersity. In property, superior gas-sensing properties such as high response, rapid response-recovery time, and good selectivity have also been shown to ethanol at an optimal working temperature of as low as 280 °C. It indicates that the as-prepared SnO{sub 2} nanocubes are promising for gas sensors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Rapid assessment of mid-infrared refractive index anisotropy using a prism coupler: chemical vapor deposited ZnS

A state-of-the-art mid-infrared prism coupler was used to study the refractive index properties of forward-looking-infrared (FLIR) grade zinc sulfide samples prepared with unique planar grain orientations and locations with respect to the CVD growth axis. This study was motivated by prior photoluminescence and x-ray diffraction measurements that suggested refractive index may vary according to grain orientation. Measurements were conducted to provide optical dispersion and thermal index (dn/dT) data at discrete laser wavelengths between 0.633 and 10.591 {mu}m at two temperature set points (30 C and 90 C). Refractive index measurements between samples exhibited an average standard deviation comparable to the uncertainty of the prism coupler measurement (0.0004 refractive index units), suggesting that the variation in refractive index as a function of planar grain orientation and CVD deposition time is negligible, and should have no impact on subsequent optical designs. Measured dispersion data at mid-infrared wavelengths was found to agree well with prior published measurements.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Synthesis of graphene platelets by chemical and electrochemical route

Graphical abstract: A schematic showing the overall reduction process of graphite to reduced graphene platelets by chemical and electrochemical route. - Highlights: • Graphene was prepared by diverse routes viz. chemical and electrochemical methods. • NaBH{sub 4} was effective for removing oxygen functional groups from graphene oxide. • Sodium borohydride reduced graphene oxide (SRGO) showed high specific capacitance. • Electrochemical rendered a cheap route for production of graphene in powder form. - Abstract: Graphene platelets were synthesized from graphene oxide by chemical and electrochemical route. Under the chemical method, sodium borohydride and hydrazine chloride were used as reductants to produce graphene. In this paper, a novel and cost effective electrochemical method, which can simplify the process of reduction on a larger scale, is demonstrated. The electrochemical method proposed in this paper produces graphene in powder form with good yield. The atomic force microscopic images confirmed that the graphene samples prepared by all the routes have multilayers of graphene. The electrochemical process provided a new route to make relatively larger area graphene sheets, which will have interest for further patterning applications. Attempt was made to quantify the quantum of reduction using cyclic voltammetry and choronopotentiometry techniques on reduced graphene samples. As a measure in reading the specific capacitance values, a maximum specific capacitance value of 265.3 F/g was obtained in sodium borohydride reduced graphene oxide.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Mapping of lanthanide-tagged proteins on western blot paper using microextraction-inductively coupled plasma-mass spectrometry

A microextraction (ME) sampling system, paired with inductively coupled plasma-mass spectrometry (ICP-MS), was employed to spatially analyze proteins tagged with lanthanum (La), gadolinium (Gd), or terbium (Tb) on the surface of western blot paper. The proteins were covalently tagged, separated via gel electrophoresis, and transferred to western blot paper for analysis by ME-ICP-MS. The ME-ICP-MS method enables the direct sampling of the tagged species on the western blot paper, without any sample preparation. Traditionally, the tagged analyte would need to be stained, excised, and digested to be analyzed by ICP-MS for its elemental and isotopic characterization. Preliminary detection limits for the ME-ICP-MS method applied to western blot paper were established to be 564, 54, and 2.5 fg for La, Gd, and Tb, respectively. The developed ME-ICP-MS method was compared to laser ablation (LA) ICP-MS, another direct solid sampling technique; it was readily determined that ME-ICP-MS can effectively map the elemental constituents on the western blot paper with comparable analysis time and measurement sensitivity. The analysis time per 2 × 4 mm extraction is ∼1 minute; if protein spots are directly targeted (rather than systematically mapping the entire blot paper), the analysis time per protein spot is ∼1 min. This developed method proved to be fast, effective, and accessible for correlating protein molecular weight with the detection of the inorganic tagant. The ME-ICP-MS approach could be widely applicable in research areas that involve metal-tagged protein bioconjugates, such as in the development of diagnostic and therapeutic agents and other biochemical probes.

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

Probing the Surface Structure of Semiconductor Nanoparticles by DNP SENS with Dielectric Support Materials

Surface characterization is crucial for understanding how the atomic-level structure affects the chemical and photophysical properties of semiconducting nanoparticles (NPs). Solid-state nuclear magnetic resonance spectroscopy (NMR) is potentially a powerful technique for the characterization of the surface of NPs, but it is hindered by poor sensitivity. Dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP SENS) has previously been demonstrated to enhance the sensitivity of surface-selective solid-state NMR experiments by 1–2 orders of magnitude. Established sample preparations for DNP SENS experiments on NPs require the dilution of the NPs on mesoporous silica. Using hexagonal boron nitride ($h$-BN) to disperse the NPs doubles DNP enhancements and absolute sensitivity in comparison to standard protocols with mesoporous silica. Alternatively, precipitating the NPs as powders, mixing them with $h$-BN, and then impregnating the powdered mixture with radical solution leads to further 4-fold sensitivity enhancements by increasing the concentration of NPs in the final sample. This modified procedure provides a factor of 9 improvement in NMR sensitivity in comparison to previously established DNP SENS procedures, enabling challenging homonuclear and heteronuclear 2D NMR experiments on CdS, Si, and Cd 3 P 2 NPs. These experiments allow NMR signals from the surface, subsurface, and core sites to be observed and assigned. For example, we demonstrate the acquisition of DNP-enhanced 2D 113 Cd– 113 Cd correlation NMR experiments on CdS NPs and natural isotropic abundance 2D 13 C– 29 Si HETCOR of functionalized Si NPs. These experiments provide a critical understanding of NP surface structures.

36 MATERIALS SCIENCE↗
NASA NTRS2009

Presolar Organic Globules in Tagish Lake Meteorite, and other Astromaterials

Presolar grains were identified in meteorite residues 20 years ago based on their exotic isotopic compositions. Their study has provide new insights into stellar evolution and the first view of the original building blocks of the solar system. Organic matter in meteorites and IDPs is highly enriched in D/H and N-15/N-14 at micrometer scales, possibly due to presolar organic grains. These anomalies are ascribed to the partial preservation of presolar cold molecular cloud material. Identifying the carriers of these anomalies and elucidating their physical and chemical properties may give new views of interstellar chemistry and better understanding of the original components of the protosolar disk. However, identifying the carriers has been hampered by their small size and the inability to chemically isolate them. Thanks to immediate careful collection of Tagish Lake meteorite specimen, as well as major advances in nano-scale analytical techniques and advanced sample preparation, we were able to show that in the Tagish Lake meteorite, the principle carriers of these isotopic anomalies are sub-micrometer, hollow organic globules. The organic globules likely formed by photochemical processing of organic ices in a cold molecular cloud or the outermost regions of the protosolar disk. Organic globules with similar physical, chemical, and isotopic properties are also recently found from Bells CM2 carbonaceous chondrite, in IDPs and in the comet Wild-2 samples returned by Stardust. These results support the view that microscopic organic grains were widespread constituents of the protoplanetary disk. Their exotic isotopic compositions trace their origins to the outermost portions of the protosolar disk or a presolar cold molecular cloud.

Nakamura-Messenger, K.↗