Microscopy Publications

2013

Tseng CH, B Paul, C Chang, and MH Engelhard. 2013. "Continuous Precipitation of Ceria Nanoparticles from a Continuous Flow Micromixer." International Journal of Advanced Manufacturing Technology 64(1-4):579-586. doi:10.1007/s00170-012-4428-1 Abstract Cerium oxide nanoparticles were continuously precipitated from a solution of cerium(III) nitrate and ammonium hydroxide using a micro-scale T-mixer. Findings show that the method of mixing is important in the ceria precipitation process. In batch mixing and deposition, disintegration and agglomeration dominates the deposited film. In T-mixing and deposition, more uniform nanorod particles are attainable. In addition, it was found that the micromixing approach reduced the exposure of the Ce(OH)3 precipates to oxygen, yielding hydroxide precipates in place of CeO2 precipitates. Advantages of the micro-scale T-mixing approach include shorter mixing times, better control of nanoparticle shape and less agglomeration.
Miller EA, TA White, BS McDonald, and A Seifert. 2013. "Phase Contrast X-ray Imaging Signatures for Security Applications." IEEE Transactions on Nuclear Science 60(1):416-422. doi:10.1109/TNS.2012.2227803 Abstract Abstract: Differential phase contrast imaging with a grating interferometer is a promising new radiographic technique providing three distinct contrast mechanisms - absorption, phase, and scatter (or dark field) - using a conventional x-ray tube source. We investigate the signatures available in these three contrast mechanisms with attention towards potential security applications. We find that the scatter mode in particular is sensitive to textured materials, enabling lowered detection limits than absorption for materials such as powders. We investigate the length scales to which our imaging system is sensitive.
Bi Y, SP Hyun, RK Kukkadapu, and KF Hayes. 2013. "Oxidative Dissolution of UO2 in a Simulated Groundwater Containing Synthetic Nanocrystalline Mackinawite." Geochimica et Cosmochimica Acta 102:175-190. doi:10.1016/j.gca.2012.10.032 Abstract The long-term success of in situ reductive immobilization of uranium (U) depends on the stability of U(IV) precipitates (e.g., uraninite) under oxic conditions. Field and laboratory studies have implicated iron sulfide minerals as redox buffers or oxidant scavengers that may slow oxidation of reduced U(VI) solid phases by oxygen and Fe(III). Yet, the inhibition mechanism(s) and reaction rates of uraninite (UO2) oxidative dissolution by oxic species such as oxygen in FeS-bearing systems remain largely unresolved. To address this knowledge gap, abiotic batch experiments were conducted with synthetic UO2 in the presence and absence of synthetic mackinawite (FeS) under simulated groundwater conditions of pH = 7, PO2 = 0.02 atm, and PCO2 = 0.05 atm (equivalent to total dissolved carbonate of 0.01 M). The kinetic profiles of dissolved uranium indicate that FeS inhibited UO2 dissolution for 51 hr by effectively scavenging oxygen and keeping dissolved oxygen (DO) low. During this time period, oxidation of structural Fe(II) and S(-II) of FeS were found to control the DO levels, leading to the formation of iron oxyhydroxides and elemental sulfur, respectively, as verified by X-ray diffraction (XRD), Mössbauer and X-ray absorption spectroscopy (XAS). After FeS was depleted due to oxidation, DO levels increased and UO2 oxidative dissolution occurred at an initial rate of rm = 1.2 ± 0.4 ×10-8 mol•g-1•s-1, higher than rm = 5.4 ± 0.3 ×10-9 mol•g-1•s-1 in the control experiment where FeS was absent. Soluble U(VI) products were adsorbed by iron oxyhydroxides (i.e. nanogoethite and ferrihydrite) formed from FeS oxidation, which facilitated the detachment of U(VI) surface complexes and more rapid dissolution of UO2. XAS analysis confirmed the adsorption of U(VI) species, and also showed that U(VI) was not significantly incorporated into iron oxyhydroxide structure. This work reveals that both the oxygen scavenging by FeS and the adsorption of U(VI) to FeS oxidation products may be important in U reductive immobilization systems subject to redox cycling events.
Arey BW, L Kovarik, O Qafoku, Z Wang, NJ Hess, and AR Felmy. 2013. "Identification of Fragile Microscopic Structures during Mineral Transformations in Wet Supercritical CO2." Microscopy and Microanalysis 19(2):268-275. doi:10.1017/S1431927612014171 Abstract In this study we examine the nature of highly fragile reaction products that form in low water content super critical carbon dioxide (scCO2) using a combination of scanning electron microscopy/focus ion beam (SEM/FIB), confocal Raman spectroscopy, helium ion microscopy (HeIM), and transmission electron microscopy (TEM). HeIM images show these precipitates to be fragile rosettes that can readily decompose even under slight heating from an electron beam. Using the TEM revealed details on the interfacial structure between the newly formed surface precipitates and the underlying initial solid phases. The detailed microscopic analysis revealed that the growth of the precipitates either followed a tip growth mechanism with precipitates forming directly on the forsterite surface if the initial solid was non-porous (natural forsterite) or growth from the surface of the precipitates where fluid was conducted through the porous (nanoforsterite) agglomerates to the growth center. The mechanism of formation of the hydrated/hydroxylated magnesium carbonate compound (HHMC) phases offers insight into the possible mechanisms of carbonate mineral formation from scCO2 solutions which has recently received a great deal of attention as the result of the potential for CO2 to act as an atmospheric greenhouse gas and impact overall global warming. The techniques used here to examine these fragile structures an also be used to examine a wide range of fragile material surfaces. SEM and FIB technologies have now been brought together in a single instrument, which represents a powerful combination for the studies in biological, geological and materials science.
Schaef HT, BP McGrail, JS Loring, ME Bowden, BW Arey, and KM Rosso. 2013. "Forsterite [Mg2SiO4)] Carbonation in Wet Supercritical CO2: An in situ High Pressure X-Ray Diffraction Study." Environmental Science & Technology 47(1):174-181. doi:10.1021/es301126f Abstract Technological advances have been significant in recent years for managing environmentally harmful emissions (mostly CO2) resulting from combustion of fossil fuels. Deep underground geologic formations are emerging as reasonable options for long term storage of CO2 but mechanisms controlling rock and mineral stability in contact with injected supercritical fluids containing water are relatively unknown. In this paper, we discuss mineral transformation reactions occurring with forsterite (Mg2SiO4) exposed to wet supercritical CO2. Forsterite was selected as it is an important olivine group mineral present in igneous and mafic rocks and has been the subject of a large number of aqueous dissolution studies that can be compared with non-aqueous fluid tests in this study. Transformation reactions were examined by in situ high pressure x-ray diffraction in the presence of supercritical carbon dioxide (scCO2) containing dissolved water at conditions relevant to carbon sequestration. Under modest pressures (90 bar) and temperatures (50°C), scCO2 saturated with water was found to convert >70 wt% forsterite to a hydrated magnesium carbonate, nesquehonite (MgCO3 •3H2O) and magnesite (MgCO3), after 72 hours of reaction. However, comparable tests with scCO2 at only partial water saturation (82%) showed a significantly slower carbonation rate with only ~30-39 wt% conversion to nesquehonite and no evidence of the anhydrous form (MgCO3). Further decreases in water content of the scCO2 continued to reduce the extent of carbonation, until a critical moisture threshold (~30%) was crossed where forsterite no longer reacted in the presence of the wet scCO2 to form crystalline carbonates. Increasing the temperature to 75°C produced anhydrous magnesium carbonate, magnesite (MgCO3), preceded by the intermediate phase, hydromagnesite [Mg(CO3)4(OH)2 •4H2O]. Measurements conducted during in situ IR experiments at 50°C and 30% saturation identified the presence of an amorphous carbonate phase as well as the formation of a thin liquid-like water layer on the forsterite surface. The presence of this water film appears to be critical for the mineral carbonation of forsterite exposed to water bearing scCO2. In contrast, our prior studies with the mineral brucite [Mg(OH)2] showed extensive carbonation in the absence of a condensed water layer on the mineral surface. The contrasts in reaction rate and products formed demonstrated by temperature and water-content dependence highlights the importance of these kinds of studies to help enable better predictions of the long term fate of geologically stored CO2.
Shao Y, F Ding, J Xiao, J Zhang, W Xu, SK Park, J Zhang, Y Wang, and J Liu. 2013. "Making Li-air batteries rechargeable: material challenges." Advanced Functional Materials 23(8):987-1004. doi:10.1002/adfm.201200688 Abstract A Li-air battery could potentially provide three to five times higher energy density/specific energy than conventional batteries, thus enable the driving range of an electric vehicle comparable to a gasoline vehicle. However, making Li-air batteries rechargeable presents significant challenges, mostly related with materials. Herein, we discuss the key factors that influence the rechargeability of Li-air batteries with a focus on nonaqueous system. The status and materials challenges for nonaqueous rechargeable Li-air batteries are reviewed. These include electrolytes, cathode (electocatalysts), lithium metal anodes, and oxygen-selective membranes (oxygen supply from air). The perspective of rechargeable Li-air batteries is provided.
Kaur M, A Johnson, G Tian, W Jiang, L Rao, A Paszczynski, and Y Qiang. 2013. "Separation Nanotechnology of Diethylenetriaminepentaacetic Acid Bonded Magnetic Nanoparticles for Spent Nuclear Fuel." Nano Energy 2(1):124-132. doi:10.1016/j.nanoen.2012.08.005 Abstract A nanomagnetic separation method based on Diethylenetriaminepentaacetic acid (DTPA) conjugated with magnetic nanoparticles (MNPs) is studied for application in spent nuclear fuel separation. The high affinity of DTPA towards actinides aids in separation from the highly acidic medium of nuclear waste. The solubility and magnetization of particles at low pH is protected by encapsulating them in silica layer. Surface functionalization of silica coated particles with polyamines enhances the loading capacity of the chelators on MNPs. The particles were characterized before and after surface modification using transmission electron microscopy (TEM), helium ion microscopy (HIM), Fourier transform-infrared (FT-IR) spectrometry, and X-ray diffractometry. The coated and uncoated samples were studied using vibrating sample magnetometer (VSM) to understand the change in magnetic properties due to the influence of the surface functionalization. The hydrodynamic size and surface charge of the particles are investigated using Dynamic Light Scattering (DLS). The uptake behavior of Am(III), Pu(IV), U(VI), and Np(V) from 0.1M NaNO3 solution was investigated. The sorption result shows the strong affinity of DTPA towards Am(III) and Pu(IV) by extracting 97% and 80% of actinides, respectively. The high removal efficiency and fast uptake of actinides make the chelator conjugated MNPs an effective method for spent nuclear fuel separation.
Wang Y, C Zhang, N Wei, M Oostrom, TW Wietsma, X Li, and AHR Bonneville. 2013. "Experimental study of crossover from capillary to viscous fingering for supercritical CO2 - water displacement in a homogeneous pore network." Environmental Science & Technology 47(1):212-218. doi:10.1021/es3014503 Abstract Carbon sequestration in saline aquifers involves displacing resident brine from the pore space by supercritical CO2 (scCO2). The displacement process is considered unstable due to the unfavorable viscosity ratio (logM < 0). The unstable mechanisms that affect scCO2 - water displacement under reservoir conditions (i.e., 41 °C, 9 MPa) were investigated in a homogeneous micromodel. A wide range of injection rates (logCa = -7.61~-4.73) was studied in two sets of experiments: discontinuous-rate injection, where the micromodel was first cleaned and saturated with water before each injection rate was imposed, and continuous-rate injection, where the rate was increased after quasi-steady conditions were reached for a certain rate. For the discontinuous-rate experiments, capillary fingering and viscous fingering are the dominant mechanisms for low (logCa <= -6.61) and high injection rates (logCa >= -5.21), respectively. Crossover from capillary to viscous fingering was observed for logCa = -5.91~-5.21, resulting in a large decrease in scCO2 saturation. The discontinuous-rate experimental results confirmed the decrease in nonwetting fluid saturation during crossover from capillary to viscous fingering predicted by numerical simulations by Lenormand et al. (1988).1 Capillary fingering was the only mechanism that dominates all injection rates in the continuous-rate experiment, and resulted in monotonic increase in scCO2 saturation.
Abramson EH, D Imre, J Beranek, J Wilson, and A Zelenyuk. 2013. "Experimental Determination of Chemical Diffusion within Secondary Organic Aerosol Particles." Physical Chemistry Chemical Physics. PCCP 15(8):2983-2991. doi:10.1039/C2CP44013J Abstract Formation, properties, transformations, and temporal evolution of secondary organic aerosols (SOA) particles strongly depend on particle phase. Recent experimental evidence from a number of groups indicates that SOA is in a semi-solid phase, the viscosity of which remained unknown. We find that when SOA is made in the presence of vapors of volatile hydrophobic molecules the SOA particles absorb and trap them. Here, we illustrate that it is possible to measure the evaporation rate of these molecules that is determined by their diffusion in SOA, which is then used to calculate a reasonably accurate value for the SOA viscosity. We use pyrene as a tracer molecule and a-pinene SOA as an illustrative case. It takes ~24 hours for half the pyrene to evaporate to yield a viscosity of 10^8 Pa s for a-pinene. This viscosity is consistent with measurements of particle bounce and evaporation rates. We show that viscosity of 10^8 Pa s implies coalescence times of minutes, consistent with the findings that SOA particles are spherical. Similar measurements on aged SOA particles doped with pyrene yield a viscosity of 10^9 Pa s, indicating that hardening occurs with time, which is consistent with observed decrease in water uptake and evaporation rate with aging.
Sushko P, L Qiao, ME Bowden, T Varga, GJ Exarhos, FK Urban, III, D Barton, and SA Chambers. 2013. "Multiband Optical Absorption Controlled by Lattice Strain in Thin-Film LaCrO3." Physical Review Letters 110(7):077401. doi:10.1103/PhysRevLett.110.077401 Abstract Experimental measurements and ab initio modeling of the optical transitions in strained G-type antiferromagnetic LaCrO3 resolve two decades of debate regarding the magnitude of the optical band gap and the character of the corresponding transitions in this material. Using time-dependent density functional theory and accounting for thermal disorder effects, we demonstrate that the fourmost prominent low-energy absorption features are due to intra-Cr t2g {eg (2.4, 3.6 eV), inter-Crt2g {t2g (4.4 eV), and inter-ion O 2p { Cr 3d (from ˘5 eV) transitions and show that the excitation energies of the latter type can be strongly affected by the lattice strain.

Next Displaying results 1 - 10 of 1535