Nuclear wastes generated from reprocessing of used nuclear fuel tend to contain a large fraction of rare earth (RE, e.g., Nd3+), transition (TM, e.g., Mo6+, Zr4+), alkali (A, e.g., Cs+), and alkaline earth cations (AE, e.g., Ba2+, Sr2+). Various strategies have been considered for immobilizing such waste streams, varying from nominally crystal-free glass to glass-ceramic to multi-phase ceramic waste forms. For glass and glass-ceramic waste forms, the added glass-forming system is generally alkali-alkaline earth-aluminoborosilicate (i.e., Na-Ca-Al-B-Si oxide). In a US-UK collaborative project, summarized here, we investigated the glass structure and crystallization dependence on compositional changes in simulated nuclear waste glasses and glass-ceramics. Compositions ranged in complexity from five – to – eight oxides. Specifically, the roles of Mo and rare earths are investigated, since a proposed glass-ceramic waste form contains crystalline phases such as powellite [(AE,A,RE)MoO4] and oxyapatite [(RE,AE,A)10Si6O26], and the precipitation of molybdenum phases is known to be affected by the rare earth concentration in the glass. Additionally, the effects of other chemical additions have been systematically investigated, including Zr, Ru, P, and Ti. A series of studies were also undertaken to ascertain the effect of the RE size on glass structure and on partitioning to crystal phases, investigating similarities and differences in glasses containing single RE oxides of Sc, Y, La, Ce, Nd, Sm, Er, Yb, or Lu. Finally, the effect of charge compensation was investigated by considering not only the commonly assessed peralkaline glass but also metaluminous and peraluminous compositions. Glass structure and crystallization studies were conducted by spectroscopic methods (i.e., Raman, X-ray absorption, nuclear magnetic resonance (NMR), optical absorption, photoluminescence, photoluminescence excitation, X-ray photoelectron spectroscopy), microscopy (i.e., scanning electron microscopy, transmission electron microscopy, electron probe microanalysis), scattering (i.e., X-ray and neutron diffraction, small angle measurements), and physical characterization (i.e., differential thermal analysis, liquidus, viscosity, density). This paper will give an overview of the research program and some example unpublished results on glass-ceramic crystallization kinetics, microstructure, and Raman spectra, as well as some examples of the effects of rare earths on the absorption, luminescence, and NMR spectra of starting glasses. The formal collaboration described here has resulted in the generation of a large number of results, some of which are still in the process of being published as separate studies.

In the present investigation, biocomposites were synthesized from a polymeric alginate matrix in which the carrot residue and a natural bentonite (ANat / Bio) or an iron-modified clinoptilolite-type zeolite (ZFe / Bio) were supported. Their properties were evaluated adsorbents in contact with aqueous solutions of methylene blue (MB). In the first hour of contact, 46% removal was obtained for the ZFe / Bio biocomposite and 60% for the ANat / Bio biocomposite; reaching 100% removal for the ZFe / Bio biocomposite and 98% for the ANat / Bio biocomposite after 24 hours. The biocomposites were characterized by Scanning Electron Microscopy (SEM) and Fourier Transformed Infrared Spectroscopy (FTIR).

The capture of volatile radioactive iodine-129 is an important process for nuclear fission. Biphenyl-bridged wrinkled mesoporous silica shows similar performance for iodine sequestration to commercial Ag-mordenite and avoids the use of expensive silver. The biphenyl-wrinkled mesoporous silica nanoparticles function as a scaffold for biphenyl groups and also as a fluorescent indicator for the loading of iodine. The nanoparticles have a surface area of 973 m2/g and the biphenyl molecules form an electron charge-transfer complex with iodine. Iodine was loaded into the biphenyl-bridged wrinkled mesoporous silica (BWMS) at 19 ± 0.2 % loading by mass.

Either boron or nitrogen doped multilayered graphene was prepared by thermal chemical vapor deposition (CVD). Obtained heteroatom doped graphene was examined by Raman scattering, x-ray photo electron spectroscopy (XPS) and temperature dependence of sheet resistance. From the Raman scattering, obvious increase of ID/IG ratio could not be detected by boron doping, while it increased by ∼0.2 or more for nitrogen doped sample. From XPS, doping rates of boron and nitrogen were estimated to be in the range of 5∼12 at% and 1∼2 at%, respectively. XPS also showed that the boron and nitrogen atoms would locate at the doping sites of both graphitic and neighborhood of atomic defect. Magnitude of sheet resistance was decreased by either doping of boron or nitrogen.

An initial mixture of raw materials (batch) typically used for the manufacture of conventional soda-lime float glass was subjected to a mechanical activation process for 30 or 60 minutes in a planetary ball mill. An intensification of the chemical reactivity of the batch, which was directly related with the increase in the milling time, was observed. This accelerated the chemical reactions that took place during the batch melting process between sodium, calcium and magnesium carbonates and other components of the mixture, which happened at significantly lower temperatures with respect to the batch without mechanical activation. The heat of fusion of the batch, estimated using a methodology previously reported in the literature, indicated that the mechanical activation given to the initial mixture of raw materials decreased the energy consumed during the batch melting. This was also evidenced by a decrease in the temperature at which the release of CO2 ended, which was considerably larger than that previously reported in the literature based solely on the decrease in the particle size of a batch of similar composition achieved by dry sieving.

It is well known that various elements substitute for a certain sub-lattice of intermetallic compounds. There have been various experimental investigations of the effects of substituted elements on mechanical properties, however, there are few reports describing the effects of multi-element substitution. In the present study, L12-type compounds A3B (Ni3Al and Co3(Al,W)) were selected as model compounds because their substitution behavior is well known. It was reported that various elements such as Ni, Co, Cu, Pd and Pt occupy the A-site, whereas Al, Si, Ga, Ge, Ti, V, Nb, Ta, Mo, and W occupy the B-site. These elements are expected to introduce local lattice distortion, which may affect the motion of dislocations over a wide range of temperatures. Several alloys composed of five or more elements including Ni, Co, Al, Mo, and W, were prepared using an Ar-arc melting machine and heat-treated. Several alloys were found to include an (Ni, Co)3(Al, Mo, W, …)-L12 compound as a constituent phase. The nano-hardness of these L12 phases was higher than that of the high-strength Co3(Al,W)-L12 compound, confirming that multi-element substitution is an effective way to improve the mechanical properties of an intermetallic compound without decreasing the phase stability.

To improve the uniformity of type-II GaAsSb/InAs nanowires (NWs) grown on GaAs substrate using the position-controlled vapor-liquid-solid (VLS) method, the insertion of GaAs NW segments was investigated. In conventional InAs NWs grown directly on patterned GaAs substrate at 430°C, anomalous growth occurred in some pattern holes, and the proportion of holes having anomalous growth was in particular pronounced when a large Au catalyst diameter (80 nm) was employed, which indicates that the strain coming from the lattice-mismatched system affected the NW growth. With the insertion of GaAs segments, the yield of vertical NWs drastically improved for all pattern conditions. The uniformity of NWs was maintained after the growth of p-GaAsSb segments, and well-organized, two-dimensional arrays of type-II GaAsSb/InAs diode NWs were obtained. Moreover, the formation of p-n junctions at the GaAsSb/InAs interface was clearly observed using scanning capacitive microscopy. These results show that the investigated growth strategy is promising for the development of high-performance NW tunnel diodes.

Spin coating and drop casting are viable methods for rapid and low-cost additive manufacturing of components for flexible devices and sensors. We investigated the cumulative effects of layering a conductive polymer composite 2 wt% MWCNT filler in PEDOT:PSS on a Mylar substrate for application to electromagnetic interference (EMI) shielding. The optical transmittace of spin coated composite layers is 90%, 45%, and 20% with a thickness of 0.05 µm, 0.15 µm, and 0.45 µm respectively. Drop cast composite layers have 0% transmittance due to their much greater starting thickness of 4.4 µm. The addition of isopropyl alcohol (IPA) to the solution mixture and substrate heating to 40 °C improves the conductivity, and drying time of the cured composite layers to 10 min. This study shows that the cumulative effects of composite layering are additive, but the electrical properties do not scale the same way. A significant increase in the EMI SE is mainly attributed to the enhanced electrical conductivity of the composite. The insertion of a 50 µm gap in between two 15 µm composite layers accentuates the EMI shielding effectiveness (SE) significantly to a peak of 21 dB within a narrow frequency range in the Ku-band tested.

Reactions of alkali salts (nitrates, sulfates, carbonates, halides, borates) play a key role in the low temperature feed conversion occurring at the cold cap during processing of Hanford Low Activity Waste (LAW) glass melters. An alkali salt phase can sometimes form, and preferentially incorporate radionuclides of Cs, Cl, I, and Tc. During melting of the slurry feed, some of the feed components sequentially break down with increasing temperature to form gases (i.e., nitrates ➔ NOx, carbonates ➔ CO2, and boric acid ➔ H2O) or partially volatilize (halides). Sulfate, however, tends not to volatilize but has limited solubility in the final borosilicate glass waste form. To improve understanding of these low temperature processes and their composition dependencies, a scoping study was undertaken to synthesize salt systems that remain amorphous at room temperature, thus facilitating structural study. Melts of equimolar ratios of K2SO4-ZnSO4 (a known ionic glass-forming system) with added nitrates, halides, or carbonates, were melted and quenched. Some of the materials formed single phase glasses and some underwent crystallization upon quenching. Characterization of these quenched materials by thermal analysis, infrared absorption, and diffraction was performed. Addition of other anions to the sulfate base glass resulted in a distortion of the sulfate tetrahedron, as evidenced by infrared absorption. Carbonates strongly promoted crystallization, mostly of carbonate phases. Nitrates promoted crystallization of ZnO, and the nitrate volatilized with some incorporating into the glass. Halides tended to incorporate into the glass, but the small (F) and large (I) halogens promoted crystallization of sulfate-containing crystals, while moderate sized (Cl) halogens produced single-phase ionic glasses.

The effect of surface-enhanced Raman spectroscopy (SERS) was investigated in N719 dye thin films deposited on silicon wafer with a thin film of silver nanoparticles (Ag-NPs) fabricated by laser ablation in an aqueous solution, using a NdYAG laser (λ = 1064nm). Optical absorption spectroscopy of the Ag-NPs colloidal solution shows an absorption peak at λ = 400nm, associated with a localized surface plasmon resonance in the Ag-NPs. Scanning electron microscopy (SEM) reveals that these NPs have an approximately spherical shape, with their diameter being tunable by laser power intensity. Raman spectroscopy measurements were performed using low laser power to avoid damage to the N719 dye films. Thus, a small Raman signal is obtained. The Raman intensity was greatly increased when the N719 film was deposited on a substrate with a thin film of Ag-NPs due to the SERS effect. The process was also used in Rhodamine-B to clearly demonstrate the SERS effect obtained by the use of these NPs produced by laser ablation.

The catalyst ZeoSonFe(M1), mixed with hydrogen peroxide and UV light, presented the highest degradation percent within 120 minutes of treatment respect to ZeoSonFe(M2), ZeoSonFe(M3) and ZeoSonFe(M4) which accounted for 72.92, 84.27, and 72.30 %, respectively. The spectrum of UV-Vis degradation showed that the absorption main bands of IC (612 and 286 nm) decrease due to the rupture of C=C bond that belong to the chromophorous group IC. The catalyst ZeoSonFe(M1) was characterized with infrared (FTIR), Scanning Electron Microscopy (SEM) and pore diameter analysis with the BET method. To describe the kinetics of the oxidative reaction the pseudo first order model was applied.