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The Effect of Temperature on the Breakdown and Repassivation Potentials of Welded Alloy 22 In 5 M CACI2

Description: The study of the electrochemical behavior of wrought and welded Alloy 22 was carried out in 5 M CaCl{sub 2} as a function of temperatures between 45 and 120 C with Multiple Crevice Assembly (MCA) specimens. The susceptibility to corrosion was found to increase with increase in electrolyte temperature in both the wrought (in the mill annealed condition) and the welded forms of the alloy. The weld metal was found to be less susceptible to localized corrosion under the conditions tested.
Date: July 5, 2006
Creator: IIevbare, G.O.
Partner: UNT Libraries Government Documents Department

Electrostatic Modeling of Vacuum Insulator Triple Junctions

Description: A comprehensive matrix of 60 tests was designed to explore the effect of calcium chloride vs. sodium chloride and the ratio R of nitrate concentration over chloride concentration on the repassivation potential of Alloy 22. Tests were conducted using the cyclic potentiodynamic polarization (CPP) technique at 75 C and at 90 C. Results show that at a ratio R of 0.18 and higher nitrate was able to inhibit the crevice corrosion in Alloy 22 induced by chloride. Current results fail to show in a consistent way a different effect on the repassivation potential of Alloy 22 for calcium chloride solutions than for sodium chloride solutions.
Date: August 13, 2007
Creator: Tully, L. K.; White, A. D.; Goerz, D. A.; Javedani, J. B. & Houck, T. L.
Partner: UNT Libraries Government Documents Department

CERIUM AND PLUTONIUM DIOXIDE--NOTES ON REDUCTION TO MASSIVE METAL

Description: In reduction reactions of CeO/sub 2/, with calcium and a CaCl/sub 2/ flux, the use of vibrational energy was shown to have a marked effect on the yield of coalesced metal. Buttons of 40 to 50% theoretical yield were obtained from the vibrated reductions. As the flux concentration is decreased, the slag becomes more viscous containing undissolved CaO. The undissolved CaO present prevents the metal from completely coalescing, but the metal can be recovered from the slag and coalesced under CaCl/sub 2/ containing a small amount of calcium to reduce any oxide skin present. Cerium pellet yields of 50 to 60% metal were obtained by the procedure and were not difficult to handle in air. Cerium was used as a stand-in material for plutonium. (B.O.G.)
Date: February 13, 1956
Creator: Tolley, W. B.
Partner: UNT Libraries Government Documents Department

Long-Term Corrosion Behavior of Alloy 22 in 5M CaCl2 at 120 C

Description: In conditions where tight crevices exist in hot chloride containing solutions Alloy 22 may suffer crevice corrosion. The occurrence (or not) of crevice corrosion in a given environment (e.g, salt concentration and temperature), is governed by the values of the critical potential (E{sub crit}) for crevice corrosion and the corrosion potential (E{sub corr}). This paper discusses the evolution of E{sub corr} and corrosion rate (CR) of creviced Alloy 22 specimens in 5 M calcium chloride (CaCl{sub 2}) at 120 C. Tested specimens included non-creviced rods and multiple creviced assemblies (MCA) both non-welded (wrought) and welded. Results show that Alloy 22 suffers crevice corrosion under the open circuit conditions in the aerated hot CaCl{sub 2} brine. However, after more than a year of immersion the propagation of crevice corrosion was not significant. The general corrosion rate decreased or remained unchanged as the immersion time increased. For rods and MCA specimens, the corrosion rate was lower than 100 nm/year after more than a year immersion time.
Date: May 8, 2006
Creator: Estill, J.C.; Hust, G.A.; Evans, K.J.; Stuart, M.L. & Rebak, R.B.
Partner: UNT Libraries Government Documents Department

Long-Term Corrosion Behavior of Alloy 22 in 5 M CaCl2 at 120?C

Description: In conditions where tight crevices exist in hot chloride containing solutions Alloy 22 may suffer crevice corrosion. The occurrence (or not) of crevice corrosion in a given environment (e.g. salt concentration and temperature), is governed by the values of the critical potential (E{sub crit}) for crevice corrosion and the corrosion potential (E{sub corr}). This paper discusses the evolution of E{sub corr} and corrosion rate (CR) of creviced Alloy 22 specimens in 5 M calcium chloride (CaCl{sub 2}) at 120 C. Tested specimens included non-creviced rods and multiple creviced assemblies (MCA) both non-welded (wrought) and welded. Results show that Alloy 22 suffers crevice corrosion under the open circuit conditions in the aerated hot CaCl{sub 2} brine. However, after more than a year immersion the propagation of crevice corrosion was not significant. The general corrosion rate decreased or remained unchanged as the immersion time increased. For rods and MCA specimens, the corrosion rate was lower than 100 nm/year after more than a year immersion time.
Date: February 5, 2006
Creator: Estill, J C; Hust, G A; Evans, K J; Stuart, M L & Rebak, R B
Partner: UNT Libraries Government Documents Department

LOCALIZED CORROSION OF AUSTENITIC STAINLESS STEELEXPOSED TO MIXTURES OF PLUTONIUM OXIDE AND CHLORIDE SALTS

Description: Laboratory corrosion tests were conducted to investigate the corrosivity of moist plutonium oxide/chloride (PuO{sub 2}/Cl-) salt mixtures on 304L and 316L stainless steel coupons. The tests exposed flat coupons for pitting evaluation and 'teardrop' stressed coupons for stress corrosion cracking (SCC) evaluation at room temperature to various mixtures of PuO{sub 2} and chloride-bearing salts for periods up to 500 days. The two flat coupons were placed so that the solid oxide/salt mixture contacted about one half of the coupon surface. One teardrop coupon was placed in contact with solid mixture; the second teardrop was in contact with the headspace gas only. The mixtures were loaded with nominally 0.5 wt % water under a helium atmosphere. Observations of corrosion ranged from superficial staining to pitting and SCC. The extent of corrosion depended on the total salt concentration and on the composition of the salt. The most significant corrosion was found in coupons that were exposed to 98 wt % PuO{sub 2}, 2 wt % chloride salt mixtures that contained calcium chloride. SCC was observed in two 304L stainless steel teardrop coupons exposed in solid contact to a mixture of 98 wt % PuO{sub 2}, 0.9 wt % NaCl, 0.9 wt % KCl, and 0.2 wt % CaCl{sub 2}. The cracking was associated with the heat-affected zone of an autogenous weld that ran across the center of the coupon. Cracking was not observed in coupons exposed to the headspace gas, nor in coupons exposed to other mixtures with either 0.92 wt% CaCl{sub 2} or no CaCl{sub 2}. The corrosion results point to the significance of the interaction between water loading and the concentration of the hydrating salt CaCl{sub 2} in the susceptibility of austenitic stainless steels to corrosion.
Date: November 21, 2008
Creator: Zapp, P; Kerry Dunn, K; Jonathan Duffey, J; Ron Livingston, R & Zane Nelson, Z
Partner: UNT Libraries Government Documents Department

Repassivation Potential of Alloy 22 in Sodium and Calcium Chloride Brines

Description: A comprehensive matrix of 60 tests was designed to explore the effect of calcium chloride vs. sodium chloride and the ratio R of nitrate concentration over chloride concentration on the repassivation potential of Alloy 22. Tests were conducted using the cyclic potentiodynamic polarization (CPP) technique at 75 C and at 90 C. Results show that at a ratio R of 0.18 and higher nitrate was able to inhibit the crevice corrosion in Alloy 22 induced by chloride. Current results fail to show in a consistent way a different effect on the repassivation potential of Alloy 22 for calcium chloride solutions than for sodium chloride solutions.
Date: August 11, 2007
Creator: Rebak, R B; Ilevbare, G O & Carranza, R M
Partner: UNT Libraries Government Documents Department

Exhaust Fan Temperature Switch

Description: The 13000 cfm 'emergency' vent fan must be protected from over cooling which would result in a mechanical failure. Over cooling could result from a catastrophic cryogen release from the cryostat(s) or Argon Storage Dewar. In order to protect the fan, a VPT has been calibrated for -31 C to open a switch which sends a signal to allow warm gas to enter the sump by means of a motor controlled louver installed at 'sidewalk level' in the ductwork between the assembly hall and the Argon Dewar Enclosure. The bulb of the VPT is enclosed in a thermal well and will be placed in the gas stream directly above the fan. The switching unit will be mounted nearby on the wall in order to isolate it from vibrational effects. Should the fan be activated due to a cryogen release, it should not experience any problems when operating above -40 C. The switch was set and checked in a saturated calcium chloride solution cooled to -31 C by running cold gaseous Nitrogen through a copper tube coiled in a dewar. Switching temperature was measured by a thermocouple tied to the VPT bulb. The thermocouple was checked in LN2, in an ice water bath, and against an ordinary thermometer (which was assumed to be accurate to plus or minus 0.3 C) at room temperature. The results are shown below in 'Table 1' By interpolation of the data, thermocouple error at -31.0 C was found to be 0.43 C on the warm side. Since this error was small, it was ignored. 'Table 2' shows the results of the tests. Ten readings were taken with the switch wired in the 'normally open' mode. This results in a signal at room temperature. The worst deviation was 2.5 C. Three readings were then taken from the ...
Date: May 11, 1989
Creator: Ball, G. S.
Partner: UNT Libraries Government Documents Department

CONTACT ANGLE OF YUCCA MOUNTAIN WELDED TUFF WITH WATER AND BRINES

Description: A number of tests were performed to acquire contact angles between Yucca Mountain welded tuff from Topopah Springs Lower Lithophysal geologic unit and various brine solutions. The tests were performed on core disks received from Sample Management Facility (SMF), oven dried to a constant weight and the core disks vacuum saturated in: distilled water, J-13 water, calcium chloride brine and sodium chloride brine to constant weight. The contact angles were acquired from eight points on the surface of the core disks, four on rough surface, and four on polished surface. The contact angle was measured by placing a droplet of the test fluid, distilled water, J-13 water, calcium chloride brine and sodium chloride brine on the core disks. The objective of this test was to acquire contact angles as a potential input to estimating capillary forces in accumulated dust on the waste packages and drip shields slated for the proposed High-Level Radioactive Waste Repository at Yucca Mountain, Nevada. It was noted that once the droplet contacts the test surface, it continues to spread hence the contact angle continues to decrease with elapsed time. The maximum observed angle was at time 0 or when the drop contacted the rock surface. The measured contact angle, in all cases has significant scatter. In general, the time zero contact angles for core disks saturated in sodium chloride brine were smaller than those saturated in calcium chloride brine, distilled water, and J-13 water. The contact angles for samples saturated in distilled water, J-13 water and calcium chloride brine at time zero were similar. There was slight difference between the observed contact angles for smooth and rough surface of the test samples. The contact angles for smooth surfaces were smaller than for the rough surfaces.
Date: April 30, 2006
Creator: Kalia, H.
Partner: UNT Libraries Government Documents Department

Geochemistry of Natural Components in the Near-Field Environment, Yucca Mountain, Nevada

Description: The natural near-field environment in and around the emplacement drifts of the proposed nuclear waste repository at Yucca Mountain, Nevada, includes the host rock, dust, seepage water, and pore water. The chemical compositions of these components have been analyzed to provide a basis for assessing possible chemical and mineralogical reactions that may occur in and around the emplacement drifts during the heating and cooling cycle. The crystal-poor rhyolite of the Topopah Spring Tuff of Miocene age with an average silica (SiO{sub 2}) content of 76 percent will host the proposed repository. Samples of the rhyolite are relatively uniform in chemical composition as shown by an average coefficient of variation (CV) of 8.6 percent for major elements. The major component of underground dust is comminuted tuff generated during construction of the tunnel. Average CVs for major elements of dust samples collected from the main tunnel (Exploratory Studies Facility, ESF) and a cross drift (Enhanced Characterization of the Repository Block, ECRB) are 25 and 28 percent, respectively. This increased variability is due to a variable amount of dust derived from trachyte with SiO{sub 2} contents as low as 66 percent (from overlying crystal-rich members) and from surface dust with an even lower average SiO{sub 2} content of 60 percent (from the abundance of trachyte in outcrop and carbonate dust derived from nearby ranges). The composition of the water-soluble fraction of dust is of interest with regard to possible salt deliquescence on waste canisters. The nitrate-to-chloride (NO{sub 3}{sup -}/Cl{sup -}) ratio (weight) is used to assess the potential corrosive nature of the salts because an excess of NO{sub 3}{sup -} over Cl{sup -} may inhibit the formation of the more corrosive calcium chloride brines in deliquescing salts. The soluble fractions of dust samples typically have NO{sub 3}{sup -}/Cl{sup -} ratios between 1 and ...
Date: June 19, 2006
Creator: Peterman, Z.E. & Oliver, T.A.
Partner: UNT Libraries Government Documents Department

Novel Self-Thickening Chemicals for Improved Conformance Control

Description: The objective of this project is to identify single chemical agents that exhibit a desirable rheological property whereby if such a chemical is dissolved in salt water it increases the solution viscosity significantly with time. We term that behavior as 'self-thickening' and have nicknamed this as 'T85 technology'. As detailed in the original project proposal, such single chemical products can be applied to advantage as agents for selectively slowing or blocking high flow water channels in subsurface oil reservoirs. The net effect is a decrease in water and an increase in oil flow and production. The initial testing has focused on five different synthetic co-polymers that have two or more chemical groups. These chemicals were dissolved at a concentration of 2500 ppm into different salt solutions (sodium chloride, potassium chloride, and calcium chloride) that encompass a range of dissolved salt concentrations. For the sodium chloride and potassium chloride solutions the salt concentration ranged from 1-5 wt%. The calcium chloride dihydrate sample concentrations ranged from 0.1-1 wt%. One set of samples being aged at 25 C and a second set at 50 C. Viscosity measurements versus aging time show two of these agents may exhibit apparent self-thickening behavior under certain salinity and temperature conditions. Generally the effect is greater in lower salinity NaCl brines and at 25 C. Preliminary flow experiments confirm that the aged fluids exhibit increased effective viscosity while flowing through a porous medium (sand pack). These flow tests include the case of the chemical fluid being aged on the bench before injection into a sand pack, and also a second series of sand packs where fresh chemical fluid is injected and allowed to age in-situ. Thus, the results of the static ageing tests together with the flow tests are a technical validation of the T85 concept.
Date: July 18, 2011
Creator: Patrick J. Shuler, Ph.D.
Partner: UNT Libraries Government Documents Department

Raman spectroscopic studies of chemical speciation in calcium chloride melts

Description: Raman spectroscopy was applied to CaCl2 melts at 900 degrees C under both non-electrolyzed and electrolyzed conditions. The later used titania cathodes supplied by TIMET, Inc. and graphite anodes. Use of pulse-gating to collect the Raman spectra successfully eliminated any interference from black-body radiation and other stray light. The spectrum of molten CaCl2 exhibited no distinct, resolvable bands that could be correlated with a calcium chloride complex similar to MgCl42- in MgCl2 melts. Rather, the low frequency region of the spectrum was dominated by a broad “tail” arising from collective oscillations of both charge and mass in the molten salt “network.” Additions of both CaO and Ca at concentrations of a percent or two resulted in no new features in the spectra. Addition of CO2, both chemically and via electrolysis at concentrations dictated by stability and solubility at 900 degrees C and 1 bar pressure, also produced no new bands that could be correlated with either dissolved CO2 or the carbonate ion. These results indicated that Raman spectroscopy, at least under the conditions evaluated in the research, was not well suited for following the reactions and coordination chemistry of calcium ions, nor species such as dissolved metallic Ca and CO2 that are suspected to impact current efficiency in titanium electrolysis cells using molten CaCl2. Raman spectra of TIMET titania electrodes were successfully obtained as a function of temperature up to 900 degrees C, both in air and in-situ in CaCl2 melts. However, spectra of these electrodes could only be obtained when the material was in the unreduced state. When reduced, either with hydrogen or within an electrolysis cell, the resulting electrodes exhibited no measurable Raman bands under the conditions used in this work.
Date: February 1, 2005
Creator: Windisch, Charles F. & Lavender, Curt A.
Partner: UNT Libraries Government Documents Department

ASSESSMENT OF RESIDUAL STRESSES IN SRS AND HANFORD 3013 INNER AND CONVENIENCE CANS

Description: Chloride stress corrosion cracking (SCC) is a plausible corrosion mechanism for the stainless steel 3013 containers during their lifetime for plutonium material storage if sufficient electrolyte is present within the container. Contributing factors for SCC, such as fabrication and welding residual stresses, are present in the 3013 cans. Convenience and inner cans from both Hanford and SRS are made by a flow form process, which cold works the stainless steel during fabrication. Additionally, the inner cans also are sealed at the can top with a closure weld to the sealing plug. Only SRS and Hanford were tested since moisture levels were significant for SCC. As part of the 3013 corrosion plan for FY09, testing in a boiling magnesium chloride solution was performed on actual 3013 convenience and inner cans to determine if the residual stresses were sufficient for the initiation and propagation of SCC. Additional testing in a 40% calcium chloride solution was also performed on 304L stainless steel SCC coupons, i.e. stressed teardrop-shaped samples (teardrops), and an inner can welded top to provide comparative results and to assess the effect of residual stresses in a less aggressive environment. The testing performed under this task consisted of 3013 inner and convenience cans and 304L teardrops exposed to a boiling magnesium chloride solutions per ASTM G36 and a 40% calcium chloride solution at 100 C following the guidance of ASTM G123. Cracking occurred in all can types including the inner can bottom and welded top and the bottoms of the SRS and Hanford convenience cans when exposed to the boiling magnesium chloride solution at 155 C. Cracking occurred at different times indicative of the residual stress levels in the cans. 304L teardrops cracked in the shortest time interval and therefore provide a conservative estimate for can performance. Testing in a 40% ...
Date: March 1, 2009
Creator: Mickalonis, J.
Partner: UNT Libraries Government Documents Department

REACTIONS OF SODIUM PEROXIDE WITH COMPONENTS OF LEGACY PLUTONIUM MATERIALS

Description: Plutonium oxide (PuO{sub 2}) calcined at >900 C resists dissolution in nitric acid (HNO{sub 3})-potassium fluoride (KF) solutions, a common method for their dissolution. The Savannah River National Laboratory (SRNL) has developed an alternate method for large samples of PuO{sub 2}-bearing materials using sodium peroxide (Na{sub 2}O{sub 2}) fusion as a pretreatment. The products of the reaction between Na{sub 2}O{sub 2} and PuO{sub 2} have been reported in the literature. As part of the SRNL development effort, additional data about the reaction between Na{sub 2}O{sub 2} and PuO{sub 2} were required. Also needed were data concerning the reaction of Na{sub 2}O{sub 2} with other components that may be present in the feed materials. Sodium peroxide was reacted with aluminum metal (Al), beryllium metal (Be), graphite, potassium chloride (KCl), magnesium chloride (MgCl{sub 2}), and calcium chloride (CaCl{sub 2}). The paper reports and discusses the reaction products of these and related compounds with Na{sub 2}O{sub 2}.
Date: October 4, 2011
Creator: Pierce, R.; Missimer, D. & Crowder, M.
Partner: UNT Libraries Government Documents Department

Corrosion Resistances of Iron-Based Amorphous Metals with Yttrium and Tungsten Additions in Hot Calcium Chloride Brine & Natural Seawater: Fe48Mo14CR15Y2C15B6 and Variants

Description: The passive film stability of several Fe-based amorphous metal formulations have been found to be comparable to that of stainless steels and Ni-based Alloy C-22 (UNS No. N06022), based on electrochemical measurements of the passive film breakdown potential and general corrosion rates. Electrochemical studies of the passive film stability of SAM1651 are reported here. Chromium (Cr), molybdenum (Mo) and tungsten (W) provide corrosion resistance; boron (B) enables glass formation; and rare earths such as yttrium (Y) lower critical cooling rate (CCR). Yttrium-containing SAM1651, also known as SAM7 (Fe{sub 48.0}Cr{sub 15.0}Mo{sub 14.0}B{sub 6.0}C{sub 15.0}Y{sub 2.0}), has a critical cooling rate (CCR) of approximately 80 Kelvin per second, while yttrium-free SAM2X5 (Fe{sub 49.7}Cr{sub 17.7}Mn{sub 1.9}Mo{sub 7.4}W{sub 1.6}B{sub 15.2}C{sub 3.8}Si{sub 2.4}) has a higher critical cooling rate of approximately 600 Kelvin per second. SAM1651's low CCR enables it to be rendered as a completely amorphous material in practical materials processes. While the yttrium enables a low CCR to be achieved, it makes the material relatively difficult to atomize, due to increases in melt viscosity. Consequently, the powders have irregular shape, which makes pneumatic conveyance during thermal spray deposition difficult. The reference material, nickel-based Alloy C-22, is an outstanding corrosion-resistant engineering material. Even so, crevice corrosion has been observed with C-22 in hot sodium chloride environments without buffer or inhibitor. SAM1651 may also experience crevice corrosion under sufficiently harsh conditions. Both Alloy C-22 and Type 316L stainless lose their resistance to corrosion during thermal spraying, due to the formation of deleterious intermetallic phases which depletes the matrix of key alloy elements, whereas SAM1651 can be applied as coatings with the same corrosion resistance as a fully-dense completely amorphous melt-spun ribbon, provided that its amorphous nature is preserved during thermal spraying. Materials synthesis and characterization is discussed. Data showing the corrosion resistance of SAM1651 in ...
Date: October 12, 2006
Creator: Farmer, J; Haslam, J; Day, S; Lian, T; Saw, C; Hailey, P et al.
Partner: UNT Libraries Government Documents Department

Corrosion Resistances of Iron-Based Amorphous Metals with Yttrium and Tungsten Additions in Hot Calcium Chloride Brine & Natural Seawater: Fe48Mo14Cr15Y2C15B6 and W-Containing Variants

Description: Yttrium-containing SAM1651 (Fe{sub 48.0}Cr{sub 15.0}Mo{sub 14.0}B{sub 6.0}C{sub 15.0}Y{sub 2.0}), has a critical cooling rate (CCR) of approximately 80 Kelvin per second, while SAM2X5 (Fe{sub 49.7}Cr{sub 17.7}Mn{sub 1.9}Mo{sub 7.4}W{sub 1.6}B{sub 15.2}C{sub 3.8}Si{sub 2.4}) with no yttrium has a higher critical cooling rate of approximately 600 Kelvin per second. SAM1651's low CCR enables it to be rendered as a completely amorphous material in practical materials processes. Chromium (Cr), molybdenum (Mo) and tungsten (W) provide corrosion resistance; boron (B) enables glass formation; and rare earths such as yttrium (Y) lower critical cooling rate (CCR). The passive film stability of these Fe-based amorphous metal formulations have been found to be superior to that of conventional stainless steels, and comparable to that of Ni-based alloys, based on electrochemical measurements of the passive film breakdown potential and general corrosion rates.
Date: October 20, 2006
Creator: Farmer, J C; Haslam, J; Day, S; Lian, T; Saw, C; Hailey, P et al.
Partner: UNT Libraries Government Documents Department

The Preparation of Uranium

Description: The method used for the preparation of uranium metal in a fused state was reduction of uranium chloride with calcium in a refractory-lined bomb. The reaction was started by externally heating the bomb with a gas flame. The metal was obtained in a solid chunk which was covered with a layer of fused calcium chloride. The metal obtained by this process had a density of 17.6 which on remelting in a vacuum induction furnace rose to 18.8. The melting temperature of the metal was estimated to be no greater than 1400 C. The metal was malleable, and had a silvery surface when freshly cut which rapidly tarnished, becoming black in the course of a few days.
Date: August 26, 1948
Creator: Rodden, Clement J.
Partner: UNT Libraries Government Documents Department

TRANSFERENCE NUMBERS AND ION ASSOCIATION IN PURE FUSED ALKALINE EARTH CHLORIDES

Description: The transference number of the chloride ion was determined in pure fused MgCl/sub 2/, CaCl/sub 2/, SrCl/sub 2/, and BaCl/sub 2/ utili zing radioactive chloride ions in a porous quartz membrane cell. On the basis of a two-step dissociation for these salts, MCl/sub 2/ in equilibrium MCl/sup +/ + Cl/sup -/ in equilibrium Ml/sup +/ + 2Cl/sup -/, the ext ent of the second dissociation was qualitatively predicted from a consideration of the relative mobilities of the ions. (auth)
Date: March 27, 1962
Creator: Wolf, E.D. & Duke, F.R.
Partner: UNT Libraries Government Documents Department

Corrosion Effects of Calcium Chloride Injection for Mercury Control on the Pollution Control Equipment

Description: In response to the Clean Air Mercury Rule (CAMR) of 2005, Black Hills Power (BHP) initiated testing of a calcium chloride (CaCl{sub 2}) injection method in their Wygen 1 (Gillette, WY) coal-fired power plant to help lower mercury emissions. In 2006, Babcock & Wilcox (B&W) was contracted to test their CaCl{sub 2} technology in-situ by adding a CaCl{sub 2} solution onto the raw, pre-pulverized coal during normal operation of Wygen 1. Follow-up tests were conducted by BHP in 2007. Data were collected from these two time periods and analyzed by a collaborative investigation team from Western Research Institute (WRI) and the University of Wyoming (UW) to see if there were any effects on the current air pollution control systems. During a CaCl{sub 2} injection period in 2007, corrosion was monitored in the flue and recycle ash system by placing corrosion coupons in strategic locations to test if corrosion was enhanced by the CaCl{sub 2} injection. While the CaCl{sub 2} produced a reduction in stack mercury levels, there was some evidence of beneficial impacts on the removal of SO{sub 2} from the flue gas during CaCl{sub 2} injection. Data on NOx remained inconclusive. It was also discovered that corrosion was enhanced significantly in the Spray Drier Absorber (SDA) vessel and corresponding outlet ductwork during CaCl{sub 2} injections. Further studies are being carried out in the field and lab to better understand the corrosive effects of CaCl{sub 2} to help formulate operation controls to manage the increased corrosion rates.
Date: February 28, 2009
Creator: Sethi, Vijay & Sharma, M.P.
Partner: UNT Libraries Government Documents Department

Modeling acid-gas generation from boiling chloride brines

Description: This study investigates the generation of HCl and other acid gases from boiling calcium chloride dominated waters at atmospheric pressure, primarily using numerical modeling. The main focus of this investigation relates to the long-term geologic disposal of nuclear waste at Yucca Mountain, Nevada, where pore waters around waste-emplacement tunnels are expected to undergo boiling and evaporative concentration as a result of the heat released by spent nuclear fuel. Processes that are modeled include boiling of highly concentrated solutions, gas transport, and gas condensation accompanied by the dissociation of acid gases, causing low-pH condensate. Simple calculations are first carried out to evaluate condensate pH as a function of HCl gas fugacity and condensed water fraction for a vapor equilibrated with saturated calcium chloride brine at 50-150 C and 1 bar. The distillation of a calcium-chloride-dominated brine is then simulated with a reactive transport model using a brine composition representative of partially evaporated calcium-rich pore waters at Yucca Mountain. Results show a significant increase in boiling temperature from evaporative concentration, as well as low pH in condensates, particularly for dynamic systems where partial condensation takes place, which result in enrichment of HCl in condensates. These results are in qualitative agreement with experimental data from other studies. The combination of reactive transport with multicomponent brine chemistry to study evaporation, boiling, and the potential for acid gas generation at the proposed Yucca Mountain repository is seen as an improvement relative to previously applied simpler batch evaporation models. This approach allows the evaluation of thermal, hydrological, and chemical (THC) processes in a coupled manner, and modeling of settings much more relevant to actual field conditions than the distillation experiment considered. The actual and modeled distillation experiments do not represent expected conditions in an emplacement drift, but nevertheless illustrate the potential for acid-gas generation at moderate ...
Date: November 16, 2009
Creator: Zhang, Guoxiang; Spycher, Nicolas; Sonnenthal, Eric & Steefel, Carl
Partner: UNT Libraries Government Documents Department

Advanced brine chemistry program. DOE Quarterly report, January 1, 1998--March 31, 1998

Description: Due to space limitations, the Chemistry Department Computer Center put some of our software routines on an old disk. This disk subsequently crashed. Since the Center had failed to back-up this space, the routines were lost. The Center acknowledges their error and has agreed to reimburse the grant for the lost time. We are now negotiating the amount of time the lost routines represent. Fortunately, data files, input and output files, models and reports were not affected by this lost. The present assessment is that several fitting codes for creating TEQUEL models and GEOFLUIDS models were lost.Fluid studies, equations of state, enthalpy models, and software improvements are discussed.
Date: May 1, 1998
Creator: Moller, N. & Weare, J.
Partner: UNT Libraries Government Documents Department

Transportation of pyrochemical salts from Rocky Flats to Los Alamos

Description: Radioactive legacy wastes or residues are currently being stored on numerous Sites around the former Department of Energy`s (DOE) Nuclear Weapons Complex. Since most of the operating facilities were shut down and have not operated since before the declared end to the Cold War in 1993, the historical method for treating these residues no longer exists. The risk associated with continued storage of these residues will dramatically increase with time. Thus, the DOE was directed by the Defense Nuclear Facility Safety Board in its Recommendation 94-1 to address and stabilize these residues and established an eight year time frame for doing so. There are only two options available to respond to this requirement: (1) restart existing facilities to treat and package the residues for disposal or (2) transport the residues to another operating facility within the Complex where they can be treated and packaged for disposal. This paper focuses on one such residue type, pyrochemical salts, produced at one Complex site, the Rocky Flats Plant located northwest of Denver, Colorado. One option for treating the salts is their shipment to Los Alamos, New Mexico, for handling at the Plutonium Facility. The safe transportation of these salts can be accomplished at present with several shipping containers including a DOT 6M, a DOE 9968, Type A or Type B quantity 55-gallon drum overpacks, or even the TRUPACT II. The tradeoffs between each container is examined with the conclusion that none of the available shipping containers is fully satisfactory. Thus, the advantageous aspects of each container must be utilized in an integrated and efficient way to effectively manage the risk involved. 1 fig.
Date: February 1, 1997
Creator: Schreiber, S.B.
Partner: UNT Libraries Government Documents Department

Different nonideality relationships, different databases and their effects on modeling precipitation from concentrated solutions using numerical speciation codes

Description: Four simple precipitation problems are solved to examine the use of numerical equilibrium codes. The study emphasizes concentrated solutions, assumes both ideal and nonideal solutions, and employs different databases and different activity-coefficient relationships. The study uses the EQ3/6 numerical speciation codes. The results show satisfactory material balances and agreement between solubility products calculated from free-energy relationships and those calculated from concentrations and activity coefficients. Precipitates show slightly higher solubilities when the solutions are regarded as nonideal than when considered ideal, agreeing with theory. When a substance may precipitate from a solution dilute in the precipitating substance, a code may or may not predict precipitation, depending on the database or activity-coefficient relationship used. In a problem involving a two-component precipitation, there are only small differences in the precipitate mass and composition between the ideal and nonideal solution calculations. Analysis of this result indicates that this may be a frequent occurrence. An analytical approach is derived for judging whether this phenomenon will occur in any real or postulated precipitation situation. The discussion looks at applications of this approach. In the solutes remaining after the precipitations, there seems to be little consistency in the calculated concentrations and activity coefficients. They do not appear to depend in any coherent manner on the database or activity-coefficient relationship used. These results reinforce warnings in the literature about perfunctory or mechanical use of numerical speciation codes.
Date: August 1, 1996
Creator: Brown, L.F. & Ebinger, M.H.
Partner: UNT Libraries Government Documents Department

High-carbon fly-ash as a binder for iron ore pellets

Description: The goal of this project was to convert currently unusable fly-ashes into a material that can be used as a binder for iron ore. Such a binder would also be useful for other high-volume markets, including foundry sand mold binders. Previously, the investigators used fly-ash in combination with calcium hydroxide as an additive while calcium chloride was added as a hardening accelerator. However, the addition of chloride salts have a detrimental effect because chlorine causes corrosion in processing equipment. Therefore, other potential hardening accelerators were investigated during this project. During production, dried iron-ore pellets are required to have crushing strength of at least 22.2 newtons (5 pounds force) per 12.7 mm (1/2 inch) diameter pellet. The pellets are then sintered at temperatures up to 1300 C and must not exhibit a significant degree of spalling or cracking. Pellets will therefore be tested to determine whether acceptable dry crushing strengths can be achieved.
Date: September 1, 1999
Creator: Kawatra, S.K.; Eisele, T.C.; Ripke, S.J. & Ramirez, G.
Partner: UNT Libraries Government Documents Department