Gregory R. Lumpkin

Micro- and nanochemistry of fly ash from a coal-fired power plant

Abstract Fly ash from a coal-fired power plant was investigated to obtain detailed information on its physical and chemical properties, and to gain an understanding of potential environmental and health impacts associated with its disposal in landfills. The studied material was produced through combustion of Illinois Basin coal and trapped within the power plant by an electrostatic precipitator. It is a finegrained, low-Ca fly ash containing primarily SiO2, Al2O3, and Fe2O3, and is enriched in many toxic elements (e.g., Be, Zn, As, Cd, Tl, Pb, and U) by a factor of up to 30 relative to coal. The ash consists of mainly hematite, magnetite, mullite, quartz, and amorphous material. These constituents occur mostly as spherical particles with diameters of less than 13 μm. We examined the physical, chemical, and structural characteristics of individual fly ash particles by scanning and transmission electron microscopy and electron probe microanalysis. The results demonstrate that, with the exception of complex plerospheres, individual particles are chemically fairly homogeneous, but a pronounced compositional variation exists among particles with similar physical and structural attributes. Electron microprobe data document that several trace elements, including U, are partitioned into the Ferich particles. Transmission electron microscopy revealed that various types of small (<1 μm) crystalline Ca-rich phases, including lime, are attached to the glass spheres, particularly the nonmagnetic glass. These crystals may contain substantial amounts of S. Even though only a few of these crystals were analyzed quantitatively, our data indicate that the Ca-rich and S-rich phases may be important hosts for trace elements such as V and Zn. The observed element partitioning and the existence of surface-attached crystals enriched in certain trace elements suggest that fly ash from coal-fired power plants might have a more deleterious environmental impact than is inferred from bulk analytical data.

In situ transmission electron microscopy investigation of radiation effects

In situ observation is of great value in the study of radiation damage utilizing electron or ion irradiation. We summarize the facilities and give examples of work found around the world. In situ observations of irradiation behavior have fallen into two broad classes. One class consists of long-term irradiation, with observations of microstructural evolution as a function of the radiation dose in which the advantage of in situ observation has been the maintenance of specimen position, orientation, and temperature. A second class has involved the recording of individual damage events in situations in which subsequent evolution would render the correct interpretation of ex situ observations impossible. In this review, examples of the first class of observation include ion-beam amorphization, damage accumulation, plastic flow, implant precipitation, precipitate evolution under irradiation, and damage recovery by thermal annealing. Examples of the second class of observation include single isolated ion impacts that produce defects in the form of dislocation loops, amorphous zones, or surface craters, and single ion impact-sputtering events. Experiments in both classes of observations attempt to reveal the kinetics underlying damage production, accumulation, and evolution.

Characterisation of the (Y1−xLax)2Ti2O7 system by powder diffraction and nuclear magnetic resonance methods

Structural characteristics of the (Y1−xLax)2Ti2O7 system have been determined using time-of-flight (TOF) neutron and constant wavelength powder X-ray diffraction (XRD), scanning electron microscopy (SEM), electron probe micro-analysis (EPMA) and 89Y (I = ½) magic-angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). Lattice parameters obtained from neutron data suggest that a pyrochlore (Fdm, Z = 8) solid solution exists from x = 0 to x = 0.134, whereupon a monoclinic La2Ti2O7-type phase (P21, Z = 4) exsolves. Both phases coexist for 0.134 ≤ n x n ≤ 0.807 and a single-phase solid solution with the monoclinic structure is stable for x > 0.807. Unit cell volumes from X-ray diffraction of samples synthesised within the pyrochlore regime show excellent agreement with the expected linear increase in unit cell volume across a solid solution, increasing from 1028.46 A3 for Y2Ti2O7 to 1037.49 A3 for (Y0.90825La0.09175)2Ti2O7. The limit of the monoclinic solid solution as observed by XRD is higher than that found from neutron diffraction (0.88 compared to 0.807), but this difference is attributed to variation in the sintering temperatures employed. Spectral analysis of NMR spectra for Y-rich compositions suggests that increasing proportions of La are incorporated onto the pyrochlore A-site randomly, up to the limit of solid solution. The NMR spectra of the monoclinic phase show four resonances – two broad and two sharp. These have been attributed to the four crystallographically distinct ‘A’-type sites within the structure. At lower Y concentrations, the sites corresponding to the broad NMR resonances are preferentially occupied. We have tentatively assigned these broad resonances to the ‘slab-edge’ sites in the monoclinic perovskite structure, based on their relatively small size and lower average coordination numbers compared to the perovskite-like sites within the centre of the slabs.

Structures of the cation-deficient perovskite Nd0.7Ti0.9Al0.1O3 from high-resolution neutron powder diffraction in combination with group-theoretical analysis

The crystal structures of Nd(0.7)Ti(0.9)Al(0.1)O3, taken to represent the ideal Nd(2/3)TiO3, have been elucidated from 4 to 1273 K using high-resolution neutron powder diffraction in combination with group-theoretical analysis. The room-temperature structure is monoclinic in C2/m, on a cell with a = 7.6764 (1), b = 7.6430 (1), c = 7.7114 (1) A, beta = 90.042 (2) degrees . Pertinent features are the layered ordering of the A-site Nd cations/vacancies along the z axis and out-of-phase tilting of the (Ti/Al)O6 octahedra around both the x and z axes. From about 750 to 1273 K, the octahedra are tilted around just one axis (x axis) perpendicular to the direction of the cation ordering, giving rise to an orthorhombic structure with space-group symmetry Cmmm.

Ion irradiation of the TiO{sub 2} polymorphs and cassiterite.

Abstract Thin crystals of rutile, brookite, anatase, and cassiterite were irradiated in situ in the transmission electron microscope using 1.0 MeV Kr ions at 50-300 K. Synthetic rutile and natural cassiterite, with 0.1-0.2 wt% impurities, remain crystalline up to a fluence of 5 × 1015 ions cm-2 without evidence for amorphization at 50 K. Natural brookite and anatase, with 0.3-0.5 wt% impurities, become amorphous at fluences of 8.1 × 1014 and 2.3 × 1014 ions cm-2, respectively. We have also studied two natural rutile samples containing ~1.7 and 1.2 wt% impurities. These samples became amorphous at 9.2 × 1014 and 8.6 × 1014 ions cm-2 at 50 K, respectively. Further analyses of the fluence-temperature data for natural brookite, rutile, and anatase give critical amorphization temperatures of 168 ± 11, 209 ± 8, and 242 ± 6 K, respectively. Results are briefly discussed with respect to several criteria for radiation resistance, including aspects of the structure, bonding, and energetics of defect formation and migration.

Crystal Chemistry and Cation Ordering in Zirconolite 2M

Structural studies of single phase or nearly single phase zirconolite ceramic samples have been conducted using electron microscopy and microanalysis, X-ray diffraction, neutron diffraction, and spectroscopic methods. We show that it is possible to produce a complete series of zirconolite 2M samples with substitution of 2Ti by Nb+Fe in the HTB layer. The samples are single phase up to about 80% Nb +Fe substitution, with the appearance of a minor perovskite phase at higher Nb+Fe levels. Electron probe microanalysis reveals that the samples are homogeneous and close to their nominal compositions, except for those containing perovskite, which have a slight excess of Zr and a deficiency in the Fe content. The lattice parameters and the positions of certain Raman bands are non-linear as a function of composition, suggesting the possibility of cation ordering over the three available Ti sites within the HTB layer. Rietveld refinement of Synchrotron X-ray powder data for the Nb+Fe end-member have been conducted for the disordered case and for six trial models each with a different ordering scheme. Results of this exercise indicate that Fe preferentially occupies the Ti2 (split) site with partial ordering of Nb and the remaining Fe over the Ti1 and Ti2 octahedra. The preference of Fe for the five coordinated Ti2 site has been confirmed by 57Fe Mossbauer spectroscopy.

Radiation Damage in Pyrochlore and Related Compounds

The radiation damage properties of synthetic pyrochlore-defect fluorite compounds containing lanthanides on the A-site and Ti, Zr, Sn, and Hf on the B-site have been studied extensively using Kr ion irradiation. Using statistical analysis, we show that the results can be quantified in terms of the critical temperature for amorphization, structural parameters, classical Pauling electronegativity difference, and defect energies. The best current model is able to predict the critical temperature to within about 80 degrees Kelvin. The model indicates that radiation tolerance is correlated with an increase in the X anion coordinate toward the value characteristic of the defect fluorite topology, a smaller unit cell dimension, and lower defect energies. Our analysis also demonstrates that radiation tolerance is promoted by an increase in the Pauling cation-anion electronegativity difference or, in other words, an increase in the ionicity of the chemical bonds. Of the two possible cation sites in ideal pyrochlore, the B-site cation appears to play the major role in bonding. This result is supported, for a subset of pyrochlore compounds, by ab initio calculations, which reveal a correlation between the Mulliken overlap populations of the B-site cation and the critical temperature.

Structural Studies of Hollandite-Based Radioactive Waste Forms

Hollandites with compositions Ba 1.2-x Cs x Mg 1.2-x/2 Ti 6.8+x/2 O 16 , and Ba 1.2-x Cs x Al 2.4-x Ti 5.6+x O 16 (x=0, 0.1, 0.25) have been synthesised using a modified alkoxide/acetate precursor route. The samples have been sintered using two procedures; hot isostatic pressing and sintering at ambient pressure. X-ray powder diffraction has shown samples from both systems to form tetragonal hollandites, with little change when pressed by both methods. Cs-133 MAS NMR spectra have been recorded showing the chemical shift in Al containing samples to be ∼250ppm, and in Mg hollandites ∼175ppm and 200ppm, with little change when prepared by both methods.

The Effect of Cs On The Structural Properties Of Barium Titanate Hollandites

Hollandite, based on Ba and Ti, has been shown to be an ideal medium by which active 135 Cs and 137 Cs can be immobilised. Diffraction measurements have shown that Cs modifies the symmetry of the material, from monoclinic to tetragonal. Experiments carried out here show the effects of Cs on two hollandite systems based on Ba-Al-Ti and Ba-Mg-Ti. Structural measurements are reported for neutron diffraction, and MAS NMR. The results show that Cs modifies the overall crystal symmetry while having little effect on the order/disorder of Al-Ti and Mg-Ti octahedra.

Solid Solubilities of Pu, U, Gd and Hf in Candidate Ceramic Nuclear Wasteforms

This goal of this research project was to determine the solid solubility of Pu, U, Gd, and Hf in candidate ceramics for immobilization of high-level nuclear waste. The experimental approach was to saturate each phase by adding more than the solid solubility limit of the given cation, using a nominated substitution scheme, and then analyzing the candidate phase that formed to evaluate the solid solubility limit under firing conditions. Confirmation that the solid solution limit had been reached insofar as other phases rich in the cation of interest was also required. The candidate phases were monazite, titanite, zirconolite, perovskite, apatite, pyrochlore, and brannerite. The valences of Pu and U were typically deduced from the firing atmosphere, and charge balancing in the candidate phase composition as evaluated from electron microscopy, although in some cases it was measured directly by x-ray absorption and diffuse reflectance spectroscopies (for U). Tetravalent Pu and U have restricted (< 0.1 formula units) solid solubility in apatite, titanite, and perovskite. Trivalent Pu has a larger solubility in apatite and perovskite than Pu4+. U3+ appears to be a credible species in reduced perovskite with a solubility of {approximately} 0.25 f.u. as opposed to {approximately} 0.05 f.u. for U4+. Pu4+ is a viable species in monazite and is promoted at lower firing temperatures ({approximately} 800 C) in an air atmosphere. Hf solubility is restricted in apatite, monazite (< 0.1 f.u.), but is {approximately} 0.2 and 0.5 f.u. in brannerite and titanite, respectively. Gd solubility is extended in all phases except for titanite ({approximately} 0.3 f.u.). U5+ was identified by DRS observations of absorption bands in the visible/near infrared photon energy ranges in brannerite and zirconolite, and U4+ in zirconolite was similarly identified.