Quarterly report of the Argonne National Laboratory Chemical Engineering Division regarding activities related to properties and handling of radioactive materials, operation of nuclear reactors, and other relevant research. This report includes studies on advanced solvent extraction techniques focused on the development of centrifugal contactors for use in Purex processes, extraction kinetics of ruthenium and zirconium in the presence of uranium, and dispersion of uranium and plutonium by fires.

To evaluate potential electrodes for molten carbonate fuel cells, we reviewed the literature pertaining to these cells and interviewed investigators working in fuel cell technology. In this critical survey, the effect of three electrode aging processes - corrosion or oxidation, sintering, and poisoning - on these potential fuel-cell electrodes is presented. It is concluded that anodes of stabilized nickel and cathodes of lithium-doped NiO are the most promising electrode materials for molten carbonate fuel cells, but that further research and development of these electrodes are needed. In particular, the effect of contaminants such as H2S and HCl on the nickel anode must be investigated, and methods to improve the physical strength and to increase the conductivity of NiO cathodes must be explored. Recommendations are given on areas of applied electrode research that should accelerate the commercialization of the molten carbonate fuel cell.

The low-cycle fatigue behavior of Type 304 stainless steel has been investigated at 593 degrees C in a dynamic vacuum of better than 1.3 x 10⁻⁶ Pa (10⁻⁸ torr). The results concerning the effects of strain range, strain rate and tensile hold time on fatigue life are presented and compared with results of similar tests performed in air and sodium environments. Under continuous symmetrical cycling, fatigue life is significantly longer in vacuum than in air; in the low strain range regime, the effect of sodium on fatigue life appears to be similar to that of vacuum. Strain rate (or frequency) strongly influences fatigue life in both air and vacuum. In compressive hold-time tests, the effect of environment on life is similar to that in a continuous-cycling test. However, tensile hold times are nearly as damaging in vacuum as in air. Thus, at least for austenitic stainless steels, the influence of the environment of fatigue life appears to depend on the loading waveshape.

Three-dimensional finite-element models for the treatment of the nonlinear, transient response of a fast breeder reactor's above-core structures are described. For purposes of treating arbitrarily large rotations, node orientations are described by unit vectors and the deformable elements are treated by a corotational formulation in which the coordinate system is embedded in the elements. Deformable elements may be connected either to nodes directly or through rigid bodies. The time integration is carried out by the Newmark beta method. These features have been incorporated to form the finite-element program SAFE/RAS (Safety Analysis by Finite Elements/Reactor Analysis and Safety Division). Computations are presented for semianalytical comparisons, simple scoping studies, and Stanford Research Institute (SRI) test comparisons.

This report describes a quasi-Eulerian method which has been incorporated into the ICECO code to study slug impact and coolant spillage problems in a fast-reactor accident. The quasi-Eulerian cells used in this method are located on the tops of the regular cells. The axial size of the quasi-Eulerian cells varies according to the gap generated at the reactor head-wall junction. Penetration holes on the cover head are modeled on the top center of the quasi-Eulerian cells. Fluid variables in these quasi-Eulerian cells also satisfy all the conservation equations. Since the boundary pressures above the quasi-Eulerian cells are determined by the movement of the moving grid, the velocity of the cover head is also included in the pressure iteration. Several examples are given to compare the results obtained by this quasi-Eulerian method with the existing experimental excursion data, as well as with the analytical and the other code solutions.

The results of simple elastic-plastic piping experiments for straight pipes and single-elbow loop systems are interpreted and evaluated. The experiments are also analyzed by the ICEPEL piping code, and the analytical results are compared against the experimental data.

A workshop was convened by the Division of Fossil Fuel Utilization of the US Department of Energy in cooperation with the Particulate and Multiphase Process Program of the National Science Foundation to identify needs for fundamental engineering support for the design of chemical reactors for processing heavy hydrocarbon liquids. The problems associated with dispersing liquid hydrocarbons in a reacting gas and mixing within the gas phase are of primary concern. The transactions of the workshop begin with an introduction to the immediate goals of the Department of Energy. Fuel cell systems and current research and development are reviewed. Modeling of combustion and the problems of soot formation and deposits in hydrocarbon fuels are next considered. The fluid mechanics of turbulent mixing and its effect on chemical reactions are then presented. Current experimental work and process development provide an update on the present state-of-the-art.

Distribution coefficients were determined for the adsorption of more than 40 elements on anion-exchange resins from mixtures of HCl (0.1 to 12M) and HF (0.1-8M). Two resins, Dowex 1 x 10, 200 to 400 mesh and Dowex 1 x 4, 100 to 200 mesh, were used. Distribution coefficients were also determined for the adsorption of many elements on both resins from 0.1 to 12M HCl and 0.1 to 12M HF. Anion exchange in the presence of HF was found useful for separating impurities from various materials for their subsequent determination, and specific procedures used in our spectrochemical laboratory for this purpose are outlined. The results of a literature search on the use of anion exchange in hydrofluoric acid and fluoride-containing media are presented in an extensive bibliography.

This report compares calculated reaction rates based on neutron-transport calculations in RZ and XY geometries with measured values from a low-power dosimetry test in EBR-II. Axial distributions of Uranium-235 and uranium-238 fission rates and uranium-238 capture rate are given for various radial locations along the length of the core and the axial reflectors, and along the length of the radial steel reflectors. Reaction rates, primarily at the reactor midplane, are given for a number of fission and capture reactions. The analytical RZ- and XY-geometry models used for the neutronics calculations are described.

Cladding failure is one of the major considerations in analysis of fuel-pin behavior during hypothetical accident transients since time, location, and nature of failure govern the early post-failure material motion and reactivity feedback. Out-of-pile thermal transient tests of both irradiated and unirradiated fast-reactor cladding show that local plastic instability, or bulging, often precedes rupture and that the extent of local instability limits the initial rip length. To investigate the details of bulge formation and growth, a perturbation analysis of the equations governing large deformation of a cylindrical shell has been developed, resulting in a set of linear differential equations for the bulge geometry. These equations have been solved along with appropriate constitutive equations and various constraints on the ends of the cladding. Sources for bulge formation that have been considered include initial geometric imperfections and thermal perturbations due to either eccentric fuel pellets or non-symmetric cooling. Of these, only the first is relevant to out-of-pile burst tests. Here it has been found that the most likely imperfection that will grow unstably to failure leads to a bulge around half the circumference with an axial length 1.1 times the deformed diameter. This is in general agreement with burst-test results. For the …

Two-step explicit numerical procedures based on the method of characteristics are presented. These procedures use four bicharacteristics equally spaced on the Mach cone. The velocity components are first obtained for the entire field by use of known initial data. Pressure is calculated in the second step in which the advanced velocity data are used. Nowhere in these procedures is an iterative scheme required. A linearized set of hyperbolic differential equations describing two-dimensional transients in slightly compressible fluid is considered for numerical solution. Detailed schemes are described in which all integration paths (bicharacteristics) remain in the coordinate planes; hence, only simple linear interpolation is required. These schemes allow time steps as large as the entire Courant step. Further, a stable new scheme is discussed in which the allowable time step can actually exceed the Courant time step. The procedure recommended for such computations was chosen after an extensive numerical experimentation that demonstrated its simplicity, efficiency, and accuracy. Exact analytical solutions are constructed and compared with numerical results to demonstrate the accuracy of the recommended scheme. 13 figures. This report presents a two-step explicit numerical procedures based on the method of characteristics are presented. These procedures use four bicharacteristics equally spaced on …

Quarterly report on activities related to the reactor safety program, analysis of safety-related critical assembly experiments, and reactor core thermal-hydraulic code development.

The principal safety-related characteristics of current CANDU-PHW power plants are described, and a distinction between those characteristics which are intrinsic to the CANDU-PHW system and those that are not is presented. An outline is given of the main features of the Canadian safety and licensing approach. Differences between the U.S. and Canadian approach to safety and licensing are discussed. Some of the main results of the safety analyses, routinely performed for CANDU-PHW reactors, are presented. U.S.-NRC General Design Criteria are evaluated as regards their applicability to CANDU-PHW reactors; vice-versa the CANDU-PHW reactor is evaluated with respect to its conformance to the U.S.-NRC General Design Criteria. A number of design modifications are proposed to be incorporated into the CANDU-PHW reactor in order to facilitate its introduction into the U.S.

Investigation of five factors affecting the aerosol generation in a glass frit bubbler system.

Three ''gassy'' irradiated uranium dioxide pins were run past failure in a 35-ms natural TREAT transient in TREAT loop Test E3 to guide in choosing between two modeling assumptions regarding energy conversion from sodium vaporization in an irradiated-oxide-fuel/coolant interaction (FCI): (1) The trapped fission gas enhances fuel fragmentation upon failure, accelerates fuel-coolant mixing, and thus promotes an energetic FCI, or, conversely, (2) the trapped fission gas blankets the fuel and reduces the rate of heat transfer to sodium, preventing an energetic FCI.

This report describes a computer program, called ANL/HIWAY, for estimating air quality levels of nonreactive pollutants produced by vehicular sources. It is valid for receptors at distances of tens to hundreds of meters, at an angle, downwind of the roadway, in relatively uncomplicated terrain. It may be used by planners to analyze the effects of a proposed roadway on adjacent air quality. The ANL/HIWAY model expands the evaluation capabilities of the EPA/HIWAY dispersion model. This report also serves as a user's manual for running the ANL/HIWAY PROGRAM. All command structures are described in detail, with sample problems exemplifying their use.

The corrosive and erosive environments at high temperatures and pressures in coal gasifiers impose severe requirements on the alloys of fabrication. A concise review of the application of ceramic coatings to resist coal-gas environments has been conducted. The purpose of this review is to explore suitable ceramic or cermet materials that may resist or retard the degradation of metal components and to summarize the state of the art of various methods of producing such coatings.

One of the important issues related to fluidized bed combustion of fossil fuels is the subsequent handling and/or treatment of the partially sulfated lime material removed from the combustor. One alternative would be to regenerate the sulfated additive to recover the sulfur, which would be stored for use, and lime that would be recycled for reuse in the combustor. It is the purpose of this report to review the development of regeneration technology which has progressed rather slowly as compared with the technology relative to the fluidized bed combustion process. The review covers research efforts specifically directed toward the regeneration of sulfated limestones plus those studies which have been made to investigate the decomposition of naturally occurring minerals of calcium sulfate. The report reviews basic thermodynamic and kinetic studies as well as laboratory, bench, and pilot scale process development studies. No attempt has been made in the review to evaluate the engineering, environmental, or economic merits of regeneration of the various regeneration schemes.

The results are discussed, and the heats and heat treatments that are most resistant to fatigue damage under these leading and environmental conditions are identified.

The Gas Cooled Fast Reactor (GCFR) Phase I Assembly is the first in a series of ZPR-9 critical assemblies designed to provide a reference set of reactor physics measurements in support of the 300 MW(e) GCFR Demonstration Plant designed by General Atomic Company. The Phase I Assembly was the first complete mockup of a GCFR core ever built. A set of basic reactor physics measurements were performed in the assembly to characterize the neutronics of the assembly and assess the impact of the neutron streaming on the various integral parameters. The analysis of the experiments was carried out using ENDF/B-IV based data and two-dimensional diffusion theory methods. The Benoist method of using directional diffusion coefficients was used to treat the anisotropic effects of neutron streaming within the framework of diffusion theory. Calculated predictions of most integral parameters in the GCFR showed the same kinds of agreements with experiment as in earlier LMFBR assemblies.

The behavior of FTR-type, mixed-oxide, pre-irradiated "high-power-structure" fuel during a simulation of an FTR loss-of-flow accident was studied in the Mark-IIA integral TREAT loop. Analysis of the data leads to a postulated scenario (sequence and timing) of events in this test. This scenario is presented, together with the calculated timing of events obtained by use of SAS code.

This effort is being directed toward support studies for the national endeavor on in situ coal gasification. This task involves the investigation of reaction-controlling variables and product distributions for the gasification of both coals and chars utilizing steam and oxygen. Included in this task is the investigation of the effects of using brackish water as the water supply. The high-pressure char gasification system has been received from the manufacturer and is currently undergoing testing. The types of experiments that would be most useful in their studies have been discussed with two of the three laboratories carrying out field tests of in-situ gasification.

The complete high-plutonium-240 fuel experiment in ZPPR assembly 4 is reviewed. Results of criticality, enrichment, small-sample perturbation, sodium void, uranium-238 Doppler, control rod substitution and reaction rate measurements are presented. Comparison of these measured values with calculated results are included where possible. The relationship between the ZPPR high-plutonium-240 fuel experiments and the results obtained in previous critical experience is considered.

Quarterly report describing the research and management efforts of the program at ANL on lithium-aluminum/metal sulfide batteries. These batteries are being developed for electric-vehicle propulsion and for stationary energy storage applications.