The nitrate to ammonia and ceramic (NAC) process for the denitration and immobilization of low-level radioactive liquid waste (LLW)

Hazardous radioactive liquid waste is the legacy of more than 50 years of plutonium production associated with the United States' nuclear weapons program. It is estimated that more than 245,000 tons of nitrate wastes are stored at facilities such as the single-shell tanks (SST) at the Hanford Site in the state of Washington, and the Melton Valley storage tanks at Oak Ridge National Laboratory (ORNL) in Tennessee. In order to develop an innovative, new technology for the destruction and immobilization of nitrate-based radioactive liquid waste, the United State Department of Energy (DOE) initiated the research project which resulted in the technology known as the Nitrate to Ammonia and Ceramic (NAC) process. However, inasmuch as the nitrate anion is highly mobile and difficult to immobilize, especially in relatively porous cement-based grout which has been used to date as a method for the immobilization of liquid waste, it presents a major obstacle to environmental clean-up initiatives. Thus, in an effort to contribute to the existing body of knowledge and enhance the efficacy of the NAC process, this research involved the experimental measurement of the rheological and heat transfer behaviors of the NAC product slurry and the determination of the optimal operating parameters for the continuous NAC chemical reaction process. Test results indicate that the NAC product slurry exhibits a typical non-Newtonian flow behavior. Correlation equations for the slurry's rheological properties and heat transfer rate in a pipe flow have been developed; these should prove valuable in the design of a full-scale NAC processing plant. The 20-percent slurry exhibited a typical dilatant (shear thickening) behavior and was in the turbulent flow regime due to its lower viscosity. The 40-percent slurry exhibited a typical pseudoplastic (shear thinning) behavior and remained in the laminar flow regime throughout its experimental range. The reactions were found to be more efficient in the lower temperature range investigated. With respect to leachability, the experimental final NAC ceramic waste form is comparable to the final product of vitrification, the technology chosen by DOE to treat these wastes. As the NAC process has the potential of reducing the volume of nitrate-based radioactive liquid waste by as much as 70 percent, it not only promises to enhance environmental remediation efforts but also effect substantial cost savings. ^

Ionized cluster beam deposition: Modeling, cluster size measurement and applications

Clusters are aggregations of atoms or molecules, generally intermediate in size between individual atoms and aggregates that are large enough to be called bulk matter. Clusters can also be called nanoparticles, because their size is on the order of nanometers or tens of nanometers. A new field has begun to take shape called nanostructured materials which takes advantage of these atom clusters. The ultra-small size of building blocks leads to dramatically different properties and it is anticipated that such atomically engineered materials will be able to be tailored to perform as no previous material could.^ The idea of ionized cluster beam (ICB) thin film deposition technique was first proposed by Takagi in 1972. It was based upon using a supersonic jet source to produce, ionize and accelerate beams of atomic clusters onto substrates in a vacuum environment. Conditions for formation of cluster beams suitable for thin film deposition have only recently been established following twenty years of effort. Zinc clusters over 1,000 atoms in average size have been synthesized both in our lab and that of Gspann. More recently, other methods of synthesizing clusters and nanoparticles, using different types of cluster sources, have come under development.^ In this work, we studied different aspects of nanoparticle beams. The work includes refinement of a model of the cluster formation mechanism, development of a new real-time, in situ cluster size measurement method, and study of the use of ICB in the fabrication of semiconductor devices.^ The formation process of the vaporized-metal cluster beam was simulated and investigated using classical nucleation theory and one dimensional gas flow equations. Zinc cluster sizes predicted at the nozzle exit are in good quantitative agreement with experimental results in our laboratory.^ A novel in situ real-time mass, energy and velocity measurement apparatus has been designed, built and tested. This small size time-of-flight mass spectrometer is suitable to be used in our cluster deposition systems and does not suffer from problems related to other methods of cluster size measurement like: requirement for specialized ionizing lasers, inductive electrical or electromagnetic coupling, dependency on the assumption of homogeneous nucleation, limits on the size measurement and non real-time capability. Measured ion energies using the electrostatic energy analyzer are in good accordance with values obtained from computer simulation. The velocity (v) is measured by pulsing the cluster beam and measuring the time of delay between the pulse and analyzer output current. The mass of a particle is calculated from m = (2E/v$\sp2).$ The error in the measured value of background gas mass is on the order of 28% of the mass of one N$\sb2$ molecule which is negligible for the measurement of large size clusters. This resolution in cluster size measurement is very acceptable for our purposes.^ Selective area deposition onto conducting patterns overlying insulating substrates was demonstrated using intense, fully-ionized cluster beams. Parameters influencing the selectivity are ion energy, repelling voltage, the ratio of the conductor to insulator dimension, and substrate thickness. ^

Continuous property measurement techniques and physics based mathematical model for frost growth control

The development of a new set of frost property measurement techniques to be used in the control of frost growth and defrosting processes in refrigeration systems was investigated. Holographic interferometry and infrared thermometry were used to measure the temperature of the frost-air interface, while a beam element load sensor was used to obtain the weight of a deposited frost layer. The proposed measurement techniques were tested for the cases of natural and forced convection, and the characteristic charts were obtained for a set of operational conditions. ^ An improvement of existing frost growth mathematical models was also investigated. The early stage of frost nucleation was commonly not considered in these models and instead an initial value of layer thickness and porosity was regularly assumed. A nucleation model to obtain the droplet diameter and surface porosity at the end of the early frosting period was developed. The drop-wise early condensation in a cold flat plate under natural convection to a hot (room temperature) and humid air was modeled. A nucleation rate was found, and the relation of heat to mass transfer (Lewis number) was obtained. It was found that the Lewis number was much smaller than unity, which is the standard value usually assumed for most frosting numerical models. The nucleation model was validated against available experimental data for the early nucleation and full growth stages of the frosting process. ^ The combination of frost top temperature and weight variation signals can now be used to control the defrosting timing and the developed early nucleation model can now be used to simulate the entire process of frost growth in any surface material. ^