DETERMINATION OF CORROSION INHIBITOR CRITERIA FOR TYPE III/IIIA TANKS DURING SALT DISSOLUTION OPERATIONS INTERIM REPORT

Preparation of high level waste for vitrification involves in part the dissolution of salt cake from the carbon steel storage tanks. During dissolution, a point is reached in which the corrosion inhibitors, hydroxide and nitrite, are diluted below established guidelines, and nitrate stress corrosion cracking (SCC) is possible. Because the addition of inhibitors may be counterproductive to process efficiency and waste minimization, corrosion testing was initiated to revisit and possibly revise the guidelines for inhibitor limits. The bases for the work summarized in this status report are results from previously-completed phases of study. In the first two phases of study, several reduced-inhibitor levels were tested in HLW simulants with nitrate concentrations ranging from 4.5 M to 8.5 M. The first two phases of work determined, among other things, the reduced-inhibitor levels and solution chemistries in which heat-treated and non-heat-treated A537 carbon steel is susceptible to SCC, crevice corrosion, and pitting. The work covered in this current task both builds on and verifies the conclusions of the previous work. The current work involves testing of low levels of inhibitors in HLW simulants with 5.5 M to 8.5 M nitrate concentrations. Stressed U-bend specimens, both polarized and non-polarized, were tested. Non-polarized U-bend testing is ongoing, with the U-bends currently in test for 100 days. The purpose of the testing is to determine SCC susceptibility in the vapor space (VS) and liquid air interface (LAI) regions of the HLW tanks under conditions expected during salt dissolution, and also to verify previous accelerated testing. The simulated wastes being tested have nitrate concentrations of 5.5 M and 8.5 M and inhibitor levels of 0.01 M/0.01 M hydroxide/nitrite and 0.1 M/ 0.1 M hydroxide/nitrite. The open circuit potential measurements being monitored and the corrosion morphology of the U-bends are in agreement with results and observations of previous phases of work. No SCC has occurred in the first 100 days of testing. The LAI specimens experienced minor corrosion at the liquid line with corrosion products visible on the weld material and in the heat-affected zones on either side of the welds. The VS specimens are more evenly and slightly more corroded. Polarized U-bend testing is complete after approximately 80 days of testing. No SCC occurred, but the results are inconclusive due to a competing, unexpected galvanic corrosion mechanism that interfered in the last 50 days of testing. No cracking was indicated during the first month. The tests will be repeated in order to satisfy the original objective which was to determine the effect of grinding HLW tank welds and heat treating the tanks had on corrosion. Both the non-polarized and polarized U-bend tests will continue. Additionally, cyclic polarization (CP) testing will be performed to examine the effects of surface oxides on corrosion and the differences in corrosion susceptibility between welded and un-welded areas

LIFE ESTIMATION OF HIGH LEVEL WASTE TANK STEEL FOR F-TANK FARM CLOSURE PERFORMANCE ASSESSMENT - 9310

High level radioactive waste (HLW) is stored in underground carbon steel storage tanks at the Savannah River Site. The underground tanks will be closed by removing the bulk of the waste, chemical cleaning, heel removal, stabilizing remaining residuals with tailored grout formulations, and severing/sealing external penetrations. The life of the carbon steel materials of construction in support of the performance assessment has been completed. The estimation considered general and localized corrosion mechanisms of the tank steel exposed to grouted conditions. A stochastic approach was followed to estimate the distributions of failures based upon mechanisms of corrosion accounting for variances in each of the independent variables. The methodology and results used for one-type of tank is presented

Photon statistics of a random laser

A general relationship is presented between the statistics of thermal radiation from a random medium and its scattering matrix S. Familiar results for black-body radiation are recovered in the limit S to 0. The mean photocount is proportional to the trace of 1-SS^dagger, in accordance with Kirchhoff's law relating emissivity and absorptivity. Higher moments of the photocount distribution are related to traces of powers of 1-SS^dagger, a generalization of Kirchhoff's law. The theory can be applied to a random amplifying medium (or "random laser") below the laser threshold, by evaluating the Bose-Einstein function at a negative temperature. Anomalously large fluctuations are predicted in the photocount upon approaching the laser threshold, as a consequence of overlapping cavity modes with a broad distribution of spectral widths.Comment: 26 pages, including 9 figure

Memorandum of Understanding Orono Bog Boardwalk Project

Memorandum of Understanding for the Orono Bog Boardwalk Project between the Orono Land Trust, Inc. Orono, Maine, College of Natural Sciences, Forestry and Agriculture of the University of Maine, City of Bangor, Maine, and Ronald B. Davis, Orono, Maine

DEVELOPMENT AND APPLICATION OF MATERIALS PROPERTIES FOR FLAW STABILITY ANALYSIS IN EXTREME ENVIRONMENT SERVICE

Discovery of aging phenomena in the materials of a structure may arise after its design and construction that impact its structural integrity. This condition can be addressed through a demonstration of integrity with the material-specific degraded conditions. Two case studies of development of fracture and crack growth property data, and their application in development of in-service inspection programs for nuclear structures in the defense complex are presented. The first case study covers the development of fracture toughness properties in the form of J-R curves for rolled plate Type 304 stainless steel with Type 308 stainless steel filler in the application to demonstrate the integrity of the reactor tanks of the heavy water production reactors at the Savannah River Site. The fracture properties for the base, weld, and heat-affected zone of the weldments irradiated at low temperatures (110-150 C) up to 6.4 dpa{sub NRT} and 275 appm helium were developed. An expert group provided consensus for application of the irradiated properties for material input to acceptance criteria for ultrasonic examination of the reactor tanks. Dr. Spencer H. Bush played a lead advisory role in this work. The second case study covers the development of fracture toughness for A285 carbon steel in high level radioactive waste tanks. The approach in this case study incorporated a statistical experimental design for material testing to address metallurgical factors important to fracture toughness. Tolerance intervals were constructed to identify the lower bound fracture toughness for material input to flaw disposition through acceptance by analysis

REMOVING SLUDGE HEELS FROM SAVANNAH RIVER SITE WASTE TANKS BY OXALIC ACID DISSOLUTION

The Savannah River Site (SRS) will remove sludge as part of waste tank closure operations. Typically the bulk sludge is removed by mixing it with supernate to produce a slurry, and transporting the slurry to a downstream tank for processing. Experience shows that a residual heel may remain in the tank that cannot be removed by this conventional technique. In the past, SRS used oxalic acid solutions to disperse or dissolve the sludge heel to complete the waste removal. To better understand the actual conditions of oxalic acid cleaning of waste from carbon steel tanks, the authors developed and conducted an experimental program to determine its effectiveness in dissolving sludge, the hydrogen generation rate, the generation rate of other gases, the carbon steel corrosion rate, the impact of mixing on chemical cleaning, the impact of temperature, and the types of precipitates formed during the neutralization process. The test samples included actual SRS sludge and simulated SRS sludge. The authors performed the simulated waste tests at 25, 50, and 75 C by adding 8 wt % oxalic acid to the sludge over seven days. They conducted the actual waste tests at 50 and 75 C by adding 8 wt % oxalic acid to the sludge as a single batch. Following the testing, SRS conducted chemical cleaning with oxalic acid in two waste tanks. In Tank 5F, the oxalic acid (8 wt %) addition occurred over seven days, followed by inhibited water to ensure the tank contained enough liquid to operate the mixer pumps. The tank temperature during oxalic acid addition and dissolution was approximately 45 C. The authors analyzed samples from the chemical cleaning process and compared it with test data. The conclusions from the work are: (1) Oxalic acid addition proved effective in dissolving sludge heels in the simulant demonstration, the actual waste demonstration, and in SRS Tank 5F. (2) The oxalic acid dissolved {approx} 100% of the uranium, {approx} 100% of the iron, and {approx} 40% of the manganese during a single contact in the simulant demonstration. (The iron dissolution may be high due to corrosion of carbon steel coupons.) (3) The oxalic acid dissolved {approx} 80% of the uranium, {approx} 70% of the iron, {approx} 50% of the manganese, and {approx} 90% of the aluminum in the actual waste demonstration for a single contact. (4) The oxalic acid dissolved {approx} 100% of the uranium, {approx} 15% of the iron, {approx} 40% of the manganese, and {approx} 80% of the aluminum in Tank 5F during the first contact cycle. Except for the iron, these results agree well with the demonstrations. The data suggest that a much larger fraction of the iron in the sludge dissolved, but it re-precipitated with the oxalate added to Tank 5F. (5) The demonstrations produced large volumes (i.e., 2-14 gallons of gas/gallon of oxalic acid) of gas (primarily carbon dioxide) by the reaction of oxalic acid with sludge and carbon steel. (6) The reaction of oxalic acid with carbon steel produced hydrogen in the simulant and actual waste demonstrations. The volume produced varied from 0.00002-0.00100 ft{sup 3} hydrogen/ft{sup 2} carbon steel. The hydrogen production proved higher in unmixed tanks than in mixed tanks