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At least 1,531 records · Page 85

Low Viscosity Imides Based on Asymmetric Oxydiphthalic Anhydride

A series of low-melt viscosity imide resins were prepared from asymmetric oxydiphthalic dianhydride (a-ODPA) and 4-phenylethynylphthalic anhydride as the endcap, along with 3,4' - oxydianiline (3,4' -ODA), 3,4' -methylenedianiline (3,4' -MDA), 3,3' -methylenedianiline (3,3' - MDA) and 3,3'-diaminobenzophenone (3,3'-DABP), using a solvent-free melt process. These imide oligomers displays low-melt viscosities (2-15 poise) at 260-280 C, which made them amenable to low-cost resin transfer molding (RTM) process. The a-ODPA based RTM resins exhibits glass transition temperatures (Tg's) in the range of 265-330 C after postcure at 343 C. The mechanical properties of these polyimide/carbon fiber composites fabricated by RTM will be discussed.

Chuang, Kathy C.↗

Process-level model evaluation: a snow and heat transfer metric

Land models require evaluation in order to understand results and guide future development. Examining functional relationships between model variables can provide insight into the ability of models to capture fundamental processes and aid in minimizing uncertainties or deficiencies in model forcing. This study quantifies the proficiency of land models to appropriately transfer heat from the soil through a snowpack to the atmosphere during the cooling season (Northern Hemisphere: October–March). Using the basic physics of heat diffusion, we investigate the relationship between seasonal amplitudes of soil versus air temperatures due to insulation from seasonal snow. Observations demonstrate the anticipated exponential relationship of attenuated soil temperature amplitude with increasing snow depth and indicate that the marginal influence of snow insulation diminishes beyond an effective snow depth of about 50 cm. A snow and heat transfer metric (SHTM) is developed to quantify model skill compared to observations. Land models within the CMIP5 experiment vary widely in SHTM scores, and deficiencies can often be traced to model structural weaknesses. The SHTM value for individual models is stable over 150 years of climate, 1850–2005, indicating that the metric is insensitive to climate forcing and can be used to evaluate each model's representation of the insulation process.

58 GEOSCIENCES↗

Production of heavy and superheavy neutron-rich nuclei in transfer reactions

The problem of production and study of heavy neutron-rich nuclei has been intensively discussed during recent years. Many reasons arouse a great interest in this problem. The present limits of the upper part of the nuclear map are very close to the {beta} stability line while the unexplored area of heavy neutron-rich nuclides (also those located along the neutron closed shell N=126 to the right-hand side of the stability line) is extremely important for nuclear astrophysic investigations and, in particular, for the understanding of the r process of astrophysical nucleogenesis. For elements with Z>100 only neutron deficient isotopes (located to the left of the stability line) have been synthesized so far. The 'northeast' area of the nuclear map can be reached neither in fusion-fission reactions nor in fragmentation processes widely used nowadays for the production of new nuclei. Multinucleon transfer processes in near barrier collisions of heavy (and very heavy, U-like) ions seem to be the only reaction mechanism allowing us to produce and explore neutron-rich heavy nuclei including those located at the superheavy island of stability. In this paper several transfer reactions for different projectile-target combinations are studied in detail. Besides the predictions for the cross sections of such processes, we also analyze the angular and energy distributions of primary and survived reaction products in the laboratory frame. These results, as well as predicted excitation functions for the yields of neutron-rich superheavy isotopes, might be useful for the design of appropriate experimental equipment and for carrying out experiments of such kind.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Active Modes and Dynamical Balances in MRI Turbulence of Keplerian Disks with a Net Vertical Magnetic Field

Her,e we studied dynamical balances in magnetorotational instability (MRI) turbulence with a net vertical field in the shearing box model of disks. Analyzing the turbulence dynamics in Fourier ($\boldsymbol{k}$-)space, we identified three types of active modes that define the turbulence characteristics. These modes have lengths similar to the box size, i.e., lie in the small wavenumber region in Fourier space labeled "the vital area" and are (i) the channel mode, uniform in the disk plane with the smallest vertical wavenumber; (ii) the zonal flow mode, azimuthally and vertically uniform with the smallest radial wavenumber; and (iii) the rest (parasitic) modes. The rest modes comprise those harmonics in the vital area whose energies reach more than 50% of the maximum spectral energy. The rest modes individually are not so significant compared to the channel and zonal flow modes; however, the combined action of their multitude is dominant over these two modes. These three mode types are governed by the interplay of the linear and nonlinear processes, leading to their interdependent dynamics. The linear processes consist of disk flow nonmodality modified classical MRI with a net vertical field. The main nonlinear process is the transfer of modes over wavevector angles in Fourier space—the transverse cascade. The channel mode exhibits episodic bursts supplied by linear MRI growth, while the nonlinear processes mostly oppose this, draining the channel energy and redistributing it to the rest modes. As for the zonal flow, it does not have a linear source and is fed by nonlinear interactions of the rest modes.

79 ASTRONOMY AND ASTROPHYSICS↗

Reversible inhibition and reactivation of electron transfer in photosystem I

In photosystem I (PSI) complexes at room temperature light induced electron transfer can proceed down multiple protein-cofactor branches, and the process can be an order of magnitude faster on one branch compared to the other. One factor that might contribute to this branch asymmetry is a tryptophan amino acid at position 673 on the psaB protein. This amino acid is located between two of the pigments involved in electron transfer on the psaB protein branch. The corresponding residue on the psaA protein branch is a glycine amino acid. Microsecond time-resolved step-scan FTIR difference spectroscopy at 77 K has been used to study isolated PSI complexes from wild type and a mutant where the tryptophan residue was changed to phenylalanine. Photoaccumulated FTIR difference spectra indicate changes in the protein structure upon mutation. In the mutant we also find that the electron transfer processes is inhibited following long periods of repetitive flash illumination at room temperature. This is due to double protonation of the pigment involved in electron transfer. However, we show that we can restore electron transfer functionality by incubating the light-treated mutant PSI samples in the presence of newly added (not protonated) pigment.

59 BASIC BIOLOGICAL SCIENCES↗

Turbulent solutions of the equations of fluid motion

Some turbulent solutions of the unaveraged Navier-Stokes equations (equations of fluid motion) are reviewed. Those equations are solved numerically in order to study the nonlinear physics of incompressible turbulent flow. Initial three-dimensional cosine velocity fluctuations and periodic boundary conditions are used in most of the work considered. The three components of the mean-square velocity fluctuations are initially equal for the conditions chosen. The resulting solutions show characteristics of turbulence such as the linear and nonlinear excitation of small-scale fluctuations. For the stronger fluctuations, the initially nonrandom flow develops into an apparently random turbulence. Thus randomness or turbulence can arise as a consequence of the structure of the Navier-Stokes equations. The cases considered include turbulence which is statistically homogeneous or inhomogeneous and isotropic or anisotropic. A mean shear is present in some cases. A statistically steady-state turbulence is obtained by using a spatially periodic body force. Various turbulence processes, including the transfer of energy between eddy sizes and between directional components, and the production, dissipation, and spatial diffusion of turbulence, are considered. It is concluded that the physical processes occurring in turbulence can be profitably studied numerically.

Deissler, R. G.↗

Turbulent solutions of equations of fluid motion

Some turbulent solutions of the unaveraged Navier-Stokes equations (equations of fluid motion) are reviewed. Those equations are solved numerically in order to study the nonlinear physics of incompressible turbulent flow. The three components of the mean-square velocity fluctuations are initially equal for the conditions chosen. The resulting solutions show characteristics of turbulence, such as the linear and nonlinear excitation of small-scale fluctuations. For the stronger fluctuations the initially nonrandom flow develops into an apparently random turbulence. The cases considered include turbulence that is statistically homogeneous or inhomogeneous and isotropic or anisotropic. A statistically steady-state turbulence is obtained by using a spatially periodic body force. Various turbulence processes, including the transfer of energy between eddy sizes and between directional components and the production, dissipation, and spatial diffusion of turbulence, are considered. It is concluded that the physical processes occurring in turbulence can be profitably studied numerically.

Deissler, R. G.↗

In-service Inspection of Radioactive Waste Tanks at the Savannah River Site – 15410

Liquid radioactive wastes from the Savannah River Site (SRS) separation process are stored in large underground carbon steel tanks. The high level wastes are processed in several of the tanks and then transferred by piping to other site facilities for further processing before they are stabilized in a vitrified or grout waste form. Based on waste removal and processing schedules, many of the tanks will be required to be in service for times exceeding the initial intended life. Until the waste is removed from storage, transferred, and processed, the materials and structures of the tanks must maintain a confinement function by providing a barrier to the environment and by maintaining acceptable structural stability during design basis events, which include loadings from both normal service and abnormal (e.g., earthquake) conditions. A structural integrity program is in place to maintain the structural and leak integrity functions of these waste tanks throughout their intended service life. In-service inspection (ISI) is an essential element of a comprehensive structural integrity program for the waste tanks at the Savannah River Site (SRS). The ISI program was developed to determine the degree of degradation the waste tanks have experienced due to service conditions. As a result of the inspections, an assessment can be made of the effectiveness of corrosion controls for the waste chemistry, which precludes accelerated localized and general corrosion of the waste tanks. Ultrasonic inspections (UT) are performed to detect and quantify the degree of general wall thinning, pitting and cracking as a measure of tank degradation. The results from these inspections through 2013, for the 27 Type III/IIIA tanks, indicate no reportable in-service corrosion degradation in the primary tank (i.e., general, pitting, or cracking). The average wall thickness for all tanks remains above the manufactured nominal thickness minus 0.25 millimeter and the largest pit identified is approximately 1.70 millimeter deep (i.e., less than 10% through-wall). Improvements to the inspection program were recently instituted to provide additional confidence in the degradation rates. Thickness measurements from a single vertical strip along the accessible height of the primary tank have been used as a baseline to compare historical measurements. Changes in wall thickness and pit depths along this vertical strip are utilized to estimate the rate of corrosion degradation. An independent review of the ISI program methodology, results, and path forward was held in August 2009. The review recommended statistical sampling of the tanks to improve the confidence of the single strip inspection program. The statistical sampling plan required that SRS increase the amount of area scanned per tank. Therefore, in addition to the baseline vertical strip that is obtained for historical comparisons, four additional randomly selected vertical strips are inspected. To date, a total of 104 independent vertical strips along the height of the primary tank have been completed. A statistical analysis of the data indicates that at this coverage level there is a 99.5% confidence level that one of the worst 5% of all the vertical strips was inspected. That is, there is a relatively high likelihood that the SRS inspection program has covered one of the most corroded areas of any of the Type III/IIIA waste tanks. These data further support the conclusion that there are no significant indications of wall thinning or pitting. Random sampling will continue to increase the confidence that one of the worst 5% has been inspected. In order to obtain the additional vertical strips, and minimize budget and schedule impacts, data collection speed for the UT system was optimized. Prior to 2009, the system collected data at a rate of 32 square centimeters per minute. The scan rate was increased to 129 - 160 square centimeters per minute by increasing the scanner step and pixel sizes in the data acquisition set-up. Laboratory testing was utilized to optimize the scan index/pixel size such that the requirements for wall thinning and pit detection were still maintained. SRS continues to evaluate improvements to ultrasonic equipment.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

In-service inspection of radioactive waste tanks at the Savannah River Site - 15410

Liquid radioactive wastes from the Savannah River Site (SRS) separation process are stored in large underground carbon steel tanks. The high level wastes are processed in several of the tanks and then transferred by piping to other site facilities for further processing before they are stabilized in a vitrified or grout waste form. Based on waste removal and processing schedules, many of the tanks, will be required to be in service for times exceeding the initial intended life. Until the waste is removed from storage, transferred, and processed, the materials and structures of the tanks must maintain a confinement function by providing a barrier to the environment and by maintaining acceptable structural stability during design basis events, which include loadings from both normal service and abnormal (e.g., earthquake) conditions. A structural integrity program is in place to maintain the structural and leak integrity functions of these waste tanks throughout their intended service life. In-service inspection (ISI) is an essential element of a comprehensive structural integrity program for the waste tanks at the Savannah River Site (SRS). The ISI program was developed to determine the degree of degradation the waste tanks have experienced due to service conditions. As a result of the inspections, an assessment can be made of the effectiveness of corrosion controls for the waste chemistry, which precludes accelerated localized and general corrosion of the waste tanks. Ultrasonic inspections (UT) are performed to detect and quantify the degree of general wall thinning, pitting and cracking as a measure of tank degradation. The results from these inspections through 2013, for the 27 Type III/IIIA tanks, indicate no reportable in-service corrosion degradation in the primary tank (i.e., general, pitting, or cracking). The average wall thickness for all tanks remains above the manufactured nominal thickness minus 0.25 millimeter and the largest pit identified is approximately 1.70 millimeter deep (i.e., less than 10% through-wall). Improvements to the inspection program were recently instituted to provide additional confidence in the degradation rates. Thickness measurements from a single vertical strip along the accessible height of the primary tank have been used as a baseline to compare historical measurements. Changes in wall thickness and pit depths along this vertical strip are utilized to estimate the rate of corrosion degradation. An independent review of the ISI program methodology, results, and path forward was held in August 2009. The review recommended statistical sampling of the tanks to improve the confidence of the single strip inspection program. The statistical sampling plan required that SRS increase the amount of area scanned per tank. Therefore, in addition to the baseline vertical strip that is obtained for historical comparisons, four additional randomly selected vertical strips are inspected. To date, a total of 104 independent vertical strips along the height of the primary tank have been completed. A statistical analysis of the data indicates that at this coverage level there is a 99.5% confidence level that one of the worst 5% of all the vertical strips was inspected. That is, there is a relatively high likelihood that the SRS inspection program has covered one of the most corroded areas of any of the Type III/IIIA waste tanks. These data further support the conclusion that there are no significant indications of wall thinning or pitting. Random sampling will continue to increase the confidence that one of the worst 5% has been inspected. In order to obtain the additional vertical strips, and minimize budget and schedule impacts, data collection speed for the UT system was optimized. Prior to 2009, the system collected data at a rate of 32 square centimeters per minute. The scan rate was increased to 129 - 160 square centimeters per minute by increasing the scanner step and pixel sizes in the data acquisition set-up. Laboratory testing was utilized to optimize the scan index/pixel size such that the requirements for wall thinning and pit detection were still maintained. SRS continues to evaluate improvements to ultrasonic equipment. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Cyber security using multi-threaded architecture data diode at the NBSR - 114

Ongoing upgrades for the control room of the National Bureau of Standards Reactor (NBSR) located at the National Institute of Standards and Technology (NIST) require the ability to collect sensor data from the secured reactor network and transfer to the outside network for trend analysis, while maintaining the security of the reactor network. To accomplish this, a data diode was created to provide a physical barrier that prevents any outside data from reaching the secured reactor network. The hardware of the data diode consists of two embedded computers, running Unix based operating systems, connected by three DB-9 serial cables. The serial cables have been modified so that only two wires, a ground and a transmission line, provide connection between the computers. The data diode relies on a multi-threaded architecture to collect and simultaneously transfer data over three serial connections. A software program, implemented in Java, has been written to request data from the digital recorders installed to monitor the NBSR process instrumentation and transfer that data across the serial connections. The data diode can collect over 1200 data points from multiple digital recorders each second. The collected data can then be stored in a relational database for later analysis. The source codes for the software are available open source on GitHub. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

RFI and SCRIMP Model Development and Verification

Vacuum-Assisted Resin Transfer Molding (VARTM) processes are becoming promising technologies in the manufacturing of primary composite structures in the aircraft industry as well as infrastructure. A great deal of work still needs to be done on efforts to reduce the costly trial-and-error methods of VARTM processing that are currently in practice today. A computer simulation model of the VARTM process would provide a cost-effective tool in the manufacturing of composites utilizing this technique. Therefore, the objective of this research was to modify an existing three-dimensional, Resin Film Infusion (RFI)/Resin Transfer Molding (RTM) model to include VARTM simulation capabilities and to verify this model with the fabrication of aircraft structural composites. An additional objective was to use the VARTM model as a process analysis tool, where this tool would enable the user to configure the best process for manufacturing quality composites. Experimental verification of the model was performed by processing several flat composite panels. The parameters verified included flow front patterns and infiltration times. The flow front patterns were determined to be qualitatively accurate, while the simulated infiltration times over predicted experimental times by 8 to 10%. Capillary and gravitational forces were incorporated into the existing RFI/RTM model in order to simulate VARTM processing physics more accurately. The theoretical capillary pressure showed the capability to reduce the simulated infiltration times by as great as 6%. The gravity, on the other hand, was found to be negligible for all cases. Finally, the VARTM model was used as a process analysis tool. This enabled the user to determine such important process constraints as the location and type of injection ports and the permeability and location of the high-permeable media. A process for a three-stiffener composite panel was proposed. This configuration evolved from the variation of the process constraints in the modeling of several different composite panels. The configuration was proposed by considering such factors as: infiltration time, the number of vacuum ports, and possible areas of void entrapment.

Loos, Alfred C.↗

Friction surfaced Stellite6 coatings

Solid state Stellite6 coatings were deposited on steel substrate by friction surfacing and compared with Stellite6 cast rod and coatings deposited by gas tungsten arc and plasma transferred arc welding processes. Friction surfaced coatings exhibited finer and uniformly distributed carbides and were characterized by the absence of solidification structure and compositional homogeneity compared to cast rod, gas tungsten arc and plasma transferred coatings. Friction surfaced coating showed relatively higher hardness. X-ray diffraction of samples showed only face centered cubic Co peaks while cold worked coating showed hexagonally close packed Co also. - Highlights: Black-Right-Pointing-Pointer Stellite6 used as coating material for friction surfacing. Black-Right-Pointing-Pointer Friction surfaced (FS) coatings compared with casting, GTA and PTA processes. Black-Right-Pointing-Pointer Finer and uniformly distributed carbides in friction surfaced coatings. Black-Right-Pointing-Pointer Absence of melting results compositional homogeneity in FS Stellite6 coatings.

36 MATERIALS SCIENCE↗

Determination of reactive mass transfer coefficients for CO 2 absorption predictions

Absorption of carbon dioxide (CO 2 ) by solvents is an important process in many practical applications such as capture of greenhouse gases from flue gas, gas processing in the chemical and petroleum industries, capture of radioactive isotopes in the nuclear cycle, etc. High pH alkaline solutions were used in this research project to capture CO 2 . The chemical reaction between CO 2 and the hydroxyl ion is known to significantly increase the absorption rate compared to the same process without chemical reaction. The aim of this report is to study the influence of the chemical reaction on the absorption rate. Because of this, the gas-liquid mass transfer coefficient was measured under reactive and nonreactive conditions. Reactive mass transfer coefficient values were higher than similar ones without chemical reaction. Under the operating conditions used in this work, the mass transfer process was found to be controlled by the liquid phase resistance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bifunction in Er{sup 3+}/Yb{sup 3+} co-doped BaTi{sub 2}O{sub 5}–Gd{sub 2}O{sub 3} glasses prepared by aerodynamic levitation method

Graphical abstract: - Highlights: • Novel BaTi{sub 2}O{sub 5}–Gd{sub 2}O{sub 3} based glasses have been prepared by aerodynamic levitation. • The obtained glasses show high thermal stability with T{sub g} = 763.3 °C. • Er{sup 3+}/Yb{sup 3+} co-doped glasses show strong upconversion based on a two-photon process. • Red emission is stronger than green emissions for EBT by high Yb{sup 3+} concentration. • Magnetic ions are paramagnetic and the distribution is homogeneous in the glasses. - Abstract: Novel Er{sup 3+}/Yb{sup 3+} co-doped BaTi{sub 2}O{sub 5}–Gd{sub 2}O{sub 3} spherical glasses have been fabricated by aerodynamic levitation method. The thermal stability, upconversion luminescence, and magnetic properties of the present glass have been studied. The glasses show high thermal stability with 763.3 °C of the onset temperature of the glass transition. Red and green emissions centered at 671 nm, 548 nm and 535 nm are obtained at 980 nm excitation. The upconversion is based on a two-photon process by energy transfer, excited-state absorption, and energy back transfer. Yb{sup 3+} ions are more than Er{sup 3+} ions in the glass, resulting in efficient energy back transfer from Er{sup 3+} to Yb{sup 3+}. So the red emission is stronger than the green emissions. Magnetization curves indicate that magnetic rare earth ions are paramagnetic and the distribution is homogeneous and random in the glass matrix. Aerodynamic levitation method is an efficient way to prepare glasses with homogeneous rare earth ions.

36 MATERIALS SCIENCE↗

Invited: uPSP Launch Vehicle Demonstration Test at NASA Ames Research Center

The Unsteady Pressure-Sensitive Paint (uPSP) Development Team outof NASA Ames Research Center (ARC) has spent the past five yearsimproving the systems and processes to advance the uPSP technology for production-level wind tunnel testing. Already considered turnkey for small-scale and research applications, development in acquisition, calibration, data transfer, and data processing were needed to be useful to customers testing at NASA wind tunnels. This development focused at ARC at the Unitary Plan Wind Tunnel (UPWT) 11-by 11-ft Transonic Wind Tunnel due to the large optical access of the test section and the NASA Advanced Supercomputer(NAS), also located at ARC. A Launch Vehicle Demonstration Test (LVDT) at the UPWT represents a milestone of this initial phase of development where several new improvements were demonstrated in a production wind tunnel environment for the first time. LVDT was conducted in April 2024 and used a 4% forebody Space Launch System (SLS) Block 1B model as the test article. Both a crew and cargo configuration were tested, with varying Mach numbers, pressures, model positions, and camera magnifications. This paper summarizes the details of the test and is part of a collection with four additional papers that provide greater detail on: high-speed lifetime methodology, spectral proper orthogonal decomposition analysis, quality of high-resolution data compared to Corcos model, and data quality, calibration, and uncertainty.

SLS↗

Light Induced Processes in CsPbBr 3 –Au Hybrid Nanocrystals: Electron Transfer and Expulsion of Au

Semiconductor–metal heterostructures such as CsPbBr 3 –Au are useful in photocatalysis. When Au nanoparticles are deposited on the CsPbBr 3 nanocrystal surface, they efficiently quench the photoluminescence of the semiconductor. This process has been studied by femtosecond transient absorption spectroscopy measurements, which indicate that electron transfer to the Au nanoparticles occurs from both hot and relaxed electrons in the conduction band of CsPbBr 3 . The electron transfer rate constant is much larger for the hot electrons compared to the relaxed electrons. Under steady state photoirradiation of CsPbBr 3 –Au heterostructure, the photogenerated electrons from the excited CsPbBr 3 nanocrystals continue to charge the Au nanoparticles. After sufficient irradiation, the gold nanoparticles dissociate from the CsPbBr 3 surface and aggregate into larger size gold nanoparticles. The expulsion of gold nanoparticles restores the original luminescence behavior of CsPbBr 3 nanocrystals. The spectroscopic and morphological studies provide insight into the expulsion of gold nanoparticles in photoirradiated CsPbBr 3 –Au heterostructures.

14 SOLAR ENERGY↗

Waste Chemistry Envelope for the Determination of Pitting Corrosion Susceptibility - 19554

Liquid radioactive wastes at the Hanford and Savannah River sites are stored in large underground carbon steel tanks. The high-level wastes are processed in several of the tanks and then transferred by piping to other site facilities for further processing before they are stabilized in a vitrified or grout waste form. Based on waste removal and processing schedules, many of the tanks, will be required to be in service for times exceeding the initial intended life (i.e., greater than 60 years). Until the waste is removed from storage, transferred, and processed, the materials and structures of the tanks must maintain a confinement function by providing a barrier to the environment and by maintaining acceptable structural stability during design basis events, which include loadings from both normal service and abnormal (e.g., earthquake) conditions. Administrative programs are in place to mitigate potential corrosion mechanisms and thereby maintain the structural and leak integrity functions of these waste tanks throughout their intended service life. Waste chemistry and temperature control are the means by which corrosion degradation of the waste tanks is minimized. Chemistry controls are based on in-situ coupon tests, waste tank experience, and laboratory testing. These requirements comprise the technical standards for corrosion control. The standards are utilized then as guidelines for operational procedures. The present waste chemistry controls for the Hanford DSTs were established in the 1980's in response to tank failures caused by stress corrosion cracking (SCC) at the DOE Savannah River Site (SRS). Portions of the SRS chemistry limits, which were developed at the Savannah River National Laboratory (SRNL) were coupled with corrosion testing results from Pacific Northwest National Laboratories (PNNL) and adopted for corrosion control of the double-shell tank (DST) waste at the Hanford Site. Since that time, the temperatures of the waste in the DSTs have decreased to less than 50 deg. C in most cases as the radioactive material has decayed. As a consequence, new chemistry controls were formulated for SCC in 2010. This testing however, did not address that potential for pitting in the supernatant and at the liquid-air interface. Indeed, initial tests indicated that the inhibitor requirements for SCC would be insufficient for the prevention of pitting. In addition to lower waste temperatures, future retrieval and process changes may impact the DST waste chemistry. Initial projections suggest that the waste chemistry of the DSTs may shift to a broader range of pH and higher aggressive anion concentrations (e.g., chloride, sulfate, etc.) than the wastes that are presently stored. Additionally, processes within the vitrification facility may result in streams that are returned to the tank farm for evaporation. These streams may also contain high concentrations of aggressive species. SRNL investigated the propensity for pitting of the carbon steel waste tanks at current and projected DST waste chemistries. A statistically designed series of tests provided a pitting factor that relates the ratio of the inhibitor species to the aggressive species and the probability of observing pitting. An acceptable pitting factor was determined and was utilized for the development of a new chemistry envelope. The new chemistry envelope was compared to the envelope that was established for SCC and was determined to be bounding. Validation of the new chemistry envelope was performed via model simulations and comparison with historical experimental results and approaches to establishing chemistry envelopes. The new chemistry envelope will eventually be part of an overall assessment of the condition of the tanks and any changes made to the overall structural integrity program for the Hanford DSTs. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

VUV Photoionization Dynamics and Reactivity of Heterogeneous Water Clusters

This feature focuses on bridging isolated water and bulk water studies. It assembles experiments and theory on water clusters, mainly probed by vacuum ultraviolet (VUV) radiation, and summarizes what the effects are of intermolecular interactions on both the spectroscopy and the VUV-induced processes in water. In particular, it highlights studies of heterogeneous water clusters─those incorporating other molecular species such as naphthalene, methane, formic acid, and glycerol─which serve as model systems to investigate the fundamental roles of water in hydrogen bonding networks, proton transfer, and astrochemical processes. These mixed clusters provide a platform to revisit the stability of protonated water clusters and compile observations of ionization-induced structural rearrangements and fragmentation, especially in systems involving hydroxyl-rich cosolvents. This feature then explores energy transfer mechanisms in molecular clusters, following VUV photoexcitation. It concludes with potential future directions. First, we investigate excited-state dynamics in molecular clusters through direct probing, complementing the synchrotron studies discussed here. Second, exploring gas-phase molecule evaporation from confined spaces and interfaces using advanced spectroscopic techniques sheds light on these ubiquitous, yet currently debated, molecular processes.

Cluster chemistry↗