Avci, Recep | Engineering Papers

DOE OSTI2019

Bulk phase resource ratio alters carbon steel corrosion rates and endogenously produced extracellular electron transfer mediators in a sulfate-reducing biofilm

Desulfovibrio alaskensis G20 biofilms were cultivated on 316 steel, 1018 steel, or borosilicate glass under steady-state conditions in electron-acceptor limiting (EAL) and electron-donor limiting (EDL) conditions with lactate and sulfate in a defined medium. Increased corrosion was observed on 1018 steel under EDL conditions compared to 316 steel, and biofilms on 1018 carbon steel under the EDL condition had at least twofold higher corrosion rates compared to the EAL condition. Furthermore, protecting the 1018 metal coupon from biofilm colonization significantly reduced corrosion, suggesting that the corrosion mechanism was enhanced through attachment between the material and the biofilm. Metabolomic mass spectrometry analyses demonstrated an increase in a flavin-like molecule under the 1018 EDL condition and sulfonates under the 1018 EAL condition. These data indicate the importance of S-cycling under the EAL condition, and that the EDL is associated with increased biocorrosion via indirect extracellular electron transfer mediated by endogenously produced flavin-like molecules.

36 MATERIALS SCIENCE↗

DOE OSTI2013

Characterization of polymeric films subjected to lithium ion beam irradiation

Two different polymeric materials that are candidate materials for use as binders for mixed uranium–plutonium oxide nuclear fuel pellets were subjected to Li ion beam irradiation, in order to simulate intense alpha irradiation. The materials (a polyethylene glycol 8000 and a microcrystalline wax) were then analyzed using a combination of mass spectrometry (MS) approaches and X-ray photoelectron spectroscopy (XPS). Samples of the irradiated PEG materials were dissolved in H2O and then analyzed using electrospray ionization-MS, which showed the formation of a series of small oligomers in addition to intact large PEG oligomers. The small oligomers were likely formed by radiation-induced homolytic scissions of the C–O and C–C bonds, which furnish radical intermediates that react by radical recombination with Hradical dot and OHradical dot. Surface analysis using SIMS revealed a heterogeneous surface that contained not only PEG-derived polymers, but also hydrocarbon-based entities that are likely surface contaminants. XPS of the irradiated PEG samples indicated the emergence of different carbon species, with peak shifts suggesting the presence of sp2 carbon atoms. Analysis of the paraffinic film using XPS showed the emergence of oxygen on the surface of the sample, and also a broadening and shifting of the C1s peak, demonstrating a change in the chemistry on the surface. The paraffinic film did not dissolve in either H2O or a H2O–methanol solution, and hence the bulk of the material could not be analyzed using electrospray. However a series of oligomers was leached from the bulk material that produced ion series in the ESI-MS analyses that were identified octylphenyl ethoxylate oligomers. Upon Li ion bombardment, these shifted to a lower average molecular weight, but more importantly showed the emergence of three new ion series that are being formed as a result of radiation damage. Surface analysis of the paraffinic polymers using SIMS produced spectra that were wholly dominated by hydrocarbon ion series, and no difference was observed between unirradiated and irradiated samples. The studies demonstrate that for the PEG-based polymers, direct evidence for radiolytic scission can be observed using ESI-MS, and suggests that both radiolytic pathways and efficiencies as a function of dose should be measurable by calibrating instrument response to the small oligomeric degradation products.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2013

Characterization of Arsenic Contamination on Rust from Ton Containers

The speciation and spatial distribution of arsenic on rusted steel surfaces affects both measurement and removal approaches. The chemistry of arsenic residing in the rust of ton containers that held the chemical warfare agents bis(2-chloroethyl)sulfide (sulfur mustard) and 2-chlorovinyldichloroarsine (Lewisite) is of particular interest, because while the agents have been decontaminated, residual arsenic could pose a health or environmental risk. The chemistry and distribution of arsenic in rust samples was probed using imaging secondary ion mass spectrometry (SIMS), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy, and scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX). Arsenic in the +3 and or +5 oxidation state is homogeneously distributed at the very top-most layer of the rust samples, and is intimately associated with iron. Sputter depth profiling followed by SIMS and XPS shows As at a depth of several nm, in some cases in a reduced form. The SEM/EDX experiments show that As is present at a depth of several microns, but is inhomogeneously distributed; most locations contained oxidized As at concentrations of a few percent, however several locations showed very high As in a metallic form. These results indicate that the rust material must be removed if the steel containers are to be cleared of arsenic.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2011

Systems and strippable coatings for decontaminating structures that include porous material

Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

36 MATERIALS SCIENCE↗

DOE OSTI2010

Methods for removing contaminant matter from a porous material

Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

Fox, Robert V↗

DOE OSTI2010

Polyphosphazine-based polymer materials

Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

36 MATERIALS SCIENCE↗

NASA NTRS2000

Mars Immunoassay Life Detection Instrument (MILDI)

The direct detection of organic biomarkers for living or fossil microbes on Mars by an in situ instrument is a worthy goal for future lander missions. We have proposed an instrument based on immunological reactions to specific antibodies to cause activation of fluorescent stains. Antibodies are raised or acquired to a variety of general and specific substances that might be in Mars soil. These antibodies are then combined with various fluorescent stains and applied to small numbered spots on a small (two to three centimeters) test plate where they become firmly attached after drying. On Mars, a sample of soil from a trench or drill core is extracted with water and/or an organic solvent that is then applied to the test plate. Any substance, which has an antibody on the test plate, will react with its antibody and activate its fluorescent stain. A small ultraviolet light source will illuminate the test plate, which is observed with a small CCD camera. The numbered spots that fluoresce indicate the presence of the tested-for substance, and the intensity indicates relative amounts. The entire instrument can be quite small and light, on the order of ten cm in each dimension. A possible choice for light source may be small UV lasers at several wavelengths. Up to 1000 different sample spots can be placed on a plate 3 cm on a side, but a more practical number might be 100. Each antibody can have a redundant position for independent verification of reaction. Some of the wells or spots can contain simply standard fluorescent stains used to detect live cells, dead cells, DNA, etc. These the stains in these spots may be directly activated; no antibodies are necessary.

McKay, David↗