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At least 1,243 records · Page 69

Elongational rheology and cohesive fracture of photo-oxidated LDPE

It was found recently that low-density polyethylene (LDPE) samples with different degrees of photo-oxidation represent an interesting system to study the transition from ductile to cohesive fracture and the aspects of the cohesive rupture in elongational flow. Sheets of LDPE were subjected to photo-oxidation in the presence of air using a xenon lamp to irradiate the samples for times between 1 day and 6 weeks. Characterisation methods included Fourier transform infrared spectroscopy, solvent extraction method, and rheology in shear and uniaxial extensional flows. Linear viscoelasticity was increasingly affected by increasing photo-oxidation due to crosslinking of LDPE, as corroborated by the carbonyl index, acid and aldehydes groups, and gel fraction. The molecular stress function model was used to quantify the experimental data, and the nonlinear model parameter β was found to be correlated with the gel content. The uniaxial data showed that the transition from ductile to cohesive fracture was shifted to lower elongational rates, the higher the gel content was. From 2 weeks photo-oxidation onwards, cohesive rupture occurred at every strain rate investigated. The true strain and true stress at cohesive fracture as well as the energy density applied to the sample up to fracture were analyzed. At low gel content, rupture was mainly determined by the melt fraction while at high gel content, rupture occurred predominantly in the gel structure. The strain at break was found to be independent of strain rate, contrary to the stress at break and the energy density. Thus, the true strain and not the stress at break or the energy density was found to be the relevant physical quantity to describe cohesive fracture behavior of photo-oxidated LDPE. The equilibrium modulus of the gel structures was correlated with the true strain at rupture. The stiffer the gel structure, the lower was the deformation tolerated before the sample breaks.

36 MATERIALS SCIENCE↗

Delamination imaging in composites using cross-correlation method by non-contact air-coupled Lamb waves

Abstract This paper presents a cross-correlation damage detection technique using damage scattered waves of all directions cross-correlate with the incident waves for delamination imaging in carbon fiber reinforced polymer (CFRP) composite plate. The presented imaging can not only detect the delamination but also precisely quantify the damage with locations and sizes. First, a CFRP composite sample with interlaminar delamination by inserting the Teflon layer is designed and manufactured in house using the hot-press machine. And a three-dimensional model of composite sample is simulated using the finite element method. Next, the cross-correlation imaging algorithm is introduced in detail, and the cross-correlation imaging proof-of-concept study is conducted with the simulated Lamb waves in the composite sample. Finally, a fully non-contact air-coupled transducer and scanning laser Doppler vibrometer system with a single-mode Lamb wave method is established to actuate and sense the interrogating Lamb waves in the structure. The imaging method is experimentally implemented for the one delamination and two delaminations imaging and quantification.

Instruments & Instrumentation↗

Initiation Thresholds and Dynamic Characteristics of an Explosion for Thin Samples of PETN-Al Composites under Laser Irradiation

In this paper, we measured thresholds H{sub cr} of explosive decomposition of thin (h = 1 mm) samples of PETN-Al composites with densities in the range of ρ = 0.9–1.7 g/cm{sup 3} and variations in the concentration of aluminum inclusions in the range of 0.025–1.0 wt % upon exposure to pulses of a neodymium laser (λ = 1064 nm, 14 ns). For each ρ, inclusion concentrations n{sub opt}, at which the threshold for explosive decomposition of H{sub cr} is minimal, are obtained. The velocities of air shock waves (ASWs) were determined depending on sample density ρ, and the times of the start of explosive decomposition were determined depending on the inclusion concentration. The amplitude (in relative units) and time shift of the maximal pressure of an ASW at the piezodetector are determined depending on sample density. It is concluded that the explosion is governed by the SW mechanism at high densities. As sample ρ decreases, the completeness of the explosion increases, with the most likely mechanism for small ρ being explosive burning. The efficiency of explosive decomposition is higher for samples with lower densities.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Controlled Solidification of Liquids Within the SFC Primary Phase Field of the “Fe{sub 2}O{sub 3}”-CaO-SiO{sub 2} System in Air

To provide fundamental information on the phases and microstructures formed during sintering, a liquid with a bulk composition within the silico ferrite of calcium (SFC) primary phase field in the ternary “Fe{sub 2}O{sub 3}”-CaO-SiO{sub 2} system in air was solidified at a controlled rate. Samples of a bulk composition with a CaO/SiO{sub 2} ratio of 4.00 and 69.24 wt pct Fe{sub 2}O{sub 3}, were cooled from 1623 K (1350 °C) at 2 K/s, with samples quenched at temperatures between 1513 K (1240 °C) to 1453 K (1180 °C). The silico ferrite of calcium and aluminium I (SFCA-I) and Ca{sub 7.2}Fe{sub 0.8}{sup 2+}Fe{sub 30}{sup 3+}O{sub 53} phases were observed to form an intergrowth (‘SFC-I’) rather than the anticipated SFC phase. Solidification was found to occur in three stages, Liquid + ‘SFC-I’, Liquid + ‘SFC-I’ + C{sub 2}S + CF{sub 2}, and C{sub 2}S + CF{sub 2} + CF, where C{sub 2}S denotes dicalcium silicate, CF denotes calcium ferrite and CF{sub 2} denotes calcium diferrite. The phases formed and the solidification sequence differ from those predicted under equilibrium and Scheil–Gulliver Cooling. Although not directly applicable to industrial operations, this research clearly shows that the formation of both the SFCA and SFCA-I phase in iron ore sinters is controlled by kinetic processes rather than equilibrium conditions.

36 MATERIALS SCIENCE↗

Radiative Ignition and Transition to Spread Investigation (RITSI)

A total of 25 experiments was conducted in the Glovebox Facility on the Third United States Microgravity payload (USMP3) mission to study the behavior of both flaming and smoldering ignition events, the transition from ignition to the flame/smoldering spread, and the flame/smoldering growth pattern in air. Twenty one of the 25 experiments were flaming experiments and the remainder were smoldering experiments. Ignition was initiated by a heated wire across a thermally thin filter paper in the middle of the sample for the two-dimensional configuration and by a focused beam from a halogen/tungsten lamp at the center of the sample for the three-dimensional configuration. The external air flow velocity was varied from 0 cm/s to 6.5 cm/s. The ignition and subsequent flame spread events were recorded by a video camera, a 35 mm camera, and 6 thermocouples (2 in the gas phase and 4 in the sample). The results indicate that non-piloted radiative ignition of the paper by external thermal radiation tends to occur more easily than in normal gravity. In the two-dimensional configuration, the transition from ignition to downstream flame spread never occurred; only the transition to upstream spread took place. In the three-dimensional configuration, a char growth pattern emerged in the shape of a fan, with the ignited area as the center of the fan and the fan spreading in the upstream direction. The internal angle of the fan increased with an increase in external flow velocity (higher flow velocity gave a more opened fan pattern). At an external flow velocity of 5 cm/s, the flame was horseshoe-shaped and the char pattern became an elongated semicircle toward upstream. It appears that the peak upstream flame spread rate was reached at a higher external velocity than for the two-dimensional flame front. Flame spread much faster along open edges of the sample paper than along the sample face, presumably due to there being larger supply of oxygen and energy feedback at the open edges than at the surface. These results indicate the possible importance of the effect of the flame front shape such as the curvature of the flame front on spread rate and flame strength. A complex, unexpected finger-shaped char growth pattern was observed during the smoldering experiment. Higher external flow velocity increased the number of localized smoldering fronts, of the char fingers they left behind, and frequency of bifurcations from the fingers. At present, it is not clear what caused such a complex char growth pattern.

Kashiwagi, Takashi↗

Approaching air buoyancy in aero/cryogel vacuum vessels

Air impermeability has been observed in low-density aerogel and cryogel materials, which has led to a series of experiments to investigate the feasibility of an air buoyant vacuum vessel, as well as the fabrication and testing of sub-buoyant prototypes. Here, bulk samples of silica aerogel were shown to isolate vacuum from ambient air for several hours with optimal vacuum isolation occurring at a density of approximately 85 mg cm –3 . It was demonstrated using polyimide aerogel and cryogel materials that the ability of these foam materials to provide an air impermeable layer between vacuum and atmosphere, in spite of being comprised of mostly void space, is related to material stiffness. It is hypothesized that this behavior is due to local deformation of the random nanostructure of the material. Spherical shell vacuum vessels were produced using the polyimide cryogel, and less than 133 Pa vacuum containment was demonstrated under active pumping. In order to approach the non-buoyant to buoyant transition for these vacuum vessels, a polyimide composite was produced using helical fibers for which preliminary mechanical testing was performed.

36 MATERIALS SCIENCE↗

Electrical characterization and water sensitivity of Sr 2 Fe 1.5 Mo 0.5 O 6-δ as a possible solid oxide fuel cell electrode

Sr 2 Fe 1.5 Mo 0.5 O 6-δ (SFMO) powders were synthesized by combustion synthesis. Porous samples were formed by uniaxial pressing of powder compacts and sintering in air. Electrical conductivity was measured by a four-point DC technique over a temperature range from 200 °C to 800 °C in air and in hydrogen. Crystal structures were investigated by X-ray diffractometry. Stability of powder samples was investigated in H 2 O-containing atmospheres. It was observed that Sr 2 Fe 1.5 Mo 0.5 O 6-δ was stable at 800 °C in water-containing atmospheres. However, it reacts with water at low temperatures. Reaction of Sr 2 Fe 1.5 Mo 0.5 O 6-δ (SFMO) with water at low temperatures is a potential shortcoming of this material for application in solid oxide fuel cells (SOFC) due to concerns regarding degradation of the electrodes at low temperatures during cycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Summary of Stack Tests at TA-16-Bldg 205: Horizontal Duct on WETF Roof

In late 2023 and early 2024, testing was done at the Weapons Engineering Tritium Facility (WETF) rooftop exhaust duct to verify that the stack sample location was in compliance with the ANSI standard for stack sampling, ANSI N13.1-1999. This ANSI standard is called out by the Clean Air Act rules for airborne radionuclide emissions from DOE facilities, 40 CFR 61 Subpart H. This sample location is designated 16020504, indicating Technical Area 16, Building 0205. The rooftop duct formerly discharged to Exhaust Stack 04, but in 2007 it was re-routed to exhaust out Building 0450, Exhaust Stack 05. For continuity, we have kept the 16020504 designation to represent this duct sample location.

54 ENVIRONMENTAL SCIENCES↗

APPLICATION OF VACUUM SALT DISTILLATION TECHNOLOGY FOR THE REMOVAL OF FLUORIDE

Vacuum distillation of chloride salts from plutonium oxide (PuO{sub 2}) and simulant PuO{sub 2} has been previously demonstrated at Department of Energy (DOE) sites using kilogram quantities of chloride salt. The apparatus for vacuum distillation contains a zone heated using a furnace and a zone actively cooled using either recirculated water or compressed air. During a vacuum distillation operation, a sample boat containing the feed material is placed into the apparatus while it is cool, and the system is sealed. The system is evacuated using a vacuum pump. Once a sufficient vacuum is attained, heating begins. Volatile salts distill from the heated zone to the cooled zone where they condense, leaving behind the non-volatile materials in the feed boat. The application of vacuum salt distillation (VSD) is of interest to the HB-Line Facility and the MOX Fuel Fabrication Facility (MFFF) at the Savannah River Site (SRS). Both facilities are involved in efforts to disposition excess fissile materials. Many of these materials contain chloride and fluoride salt concentrations which make them unsuitable for dissolution without prior removal of the chloride and fluoride salts. Between September 2009 and January 2011, the Savannah River National Laboratory (SRNL) and HB-Line designed, developed, tested, and successfully deployed a system for the distillation of chloride salts. Subsequent efforts are attempting to adapt the technology for the removal of fluoride. Fluoride salts of interest are less-volatile than the corresponding chloride salts. Consequently, an alternate approach is required for the removal of fluoride without significantly increasing the operating temperature. HB-Line Engineering requested SRNL to evaluate and demonstrate the feasibility of an alternate approach using both non-radioactive simulants and plutonium-bearing materials. Whereas the earlier developments targeted the removal of sodium chloride (NaCl) and potassium chloride (KCl), the current activities are concerned with the removal of the halide ions associated with plutonium trifluoride (PuF{sub 3}), plutonium tetrafluoride (PuF{sub 4}), calcium fluoride (CaF{sub 2}), and calcium chloride (CaCl{sub 2}). This report discusses non-radioactive testing of small-scale and pilot-scale systems and radioactive testing of a small-scale system. Experiments focused on demonstrating the chemistry for halide removal and addressing the primary engineering questions associated with a change in the process chemistry.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Pt-functionalized reduced graphene oxide for excellent hydrogen sensing at room temperature

Cost effective and faster detection of H{sub 2} has always remained a challenge. We report synthesis of reduced graphene oxide (RGO)–Pt composite and its application as highly sensitive and selective H{sub 2} sensors at room temperature. Four samples by varying the ratio of RGO and Pt were prepared to test their sensing performance. The tests were carried out in inert (N{sub 2}) ambience as well as air ambience. It was observed that the RGO:Pt (1:3) 1 h reduced sample demonstrated the best H{sub 2} sensing performance in terms of sensitivity, response time, and recovery time at room temperature. Its response varied from ∼19% (200 ppm) to 57% (5000 ppm) against H{sub 2} in air ambience. Also, the response time and recovery time of the RGO:Pt (1:3) sample were found to be as fast as 65 s and 230 s against 5000 ppm, respectively, in air ambience. In N{sub 2} ambience, the RGO:Pt (1:3) sample demonstrated the best response of −97% (500 ppm), but its recovery was found to be poor. The RGO–Pt composite formation was verified by high resolution transmission electron microscopy and X-ray photoelectron spectroscopy. The detailed physics behind the sensing mechanisms have been explained and experimentally verified in this work.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Comparison of Upper Tropospheric Water Vapor from AIRS and Cryogenic Frostpoint Hygrometers

Upper tropospheric water vapor (UTWV) from the Atmospheric Infrared Sounder (AIRS) experiment on NASA's Aqua spacecraft has the potential of addressing several important climate questions. The specified AIRS system measurement uncertainty for water vapor is 20 percent absolute averaged over 2 km layers. Cryogenic frostpoint hygrometers (CFH) are balloon-borne water vapor sensors responsive from the surface into the lower stratosphere. Several dozen coincident, collocated CFH profiles have been obtained for AlRS validation. The combination of CFH sensitivity and sample size offers a statistically compelling picture of AIRS UTWV measurement capability. We present a comparison between CFH observations and AlRS retrievals. We focus on the altitude range from the middle troposphere up to heights at the limits of AlRS sensitivity to water vapor, believed to be around 100-1 50 hPa.

validation↗

Tank 14H Preliminary Cease Waste Removal Sample Analyses

Savannah River Mission Completion Waste Removal and Tank Closure requested that Savannah River National Laboratory perform characterization analyses of Tank 14H in support of closure activities, specifically preliminary cease waste removal. This report provides important characterization of the prepared filtrate and air-dried solids in the January 2026 Tank 14H sample, HTF-14-26-1,2,3,4,5,6, for I-129, Tc-99, Cs-137, and Sr-90. The results reported here were utilized by SRMC to declare preliminary cease waste removal for Tank 14H.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Capture of Iodine from Nuclear-Fuel-Reprocessing Off-Gas: Influence of Aging on a Reduced Silver Mordenite Adsorbent after Exposure to NO/NO 2

Iodine radioisotopes released during nuclear fuel reprocessing must be removed from the off-gas stream before discharge. One promising material for iodine capture is reduced silver mordenite (Ag 0 Z). Nevertheless, the adsorbent’s capacity will degrade, or age, over time when the material is exposed to other off-gas constituents. Though the overall impact of aging is known, the underlying physical and chemical processes are not. To examine these processes, Ag 0 Z samples were prepared and aged in 2% NO 2 in dry air and in 1% NO in N 2 gas streams at 150 °C for up to six months. Aged samples were then characterized using scanning electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray absorption spectroscopy. These techniques show that aging involves two overarching processes: (i) oxidation of the silver nanoparticles present in Ag 0 Z and (ii) migration of oxidized silver into the mordenite’s inner network. Silver on the nanoparticle’s surface is oxidized through adsorption of O 2 , NO, and NO 2 . Additionally, Raman spectroscopy and X-ray absorption spectroscopy indicate that nitrates are the primary products of this adsorption. Most of these nitrates migrate into the interior of the mordenite and exchange at framework binding sites, returning silver to its unreduced state (AgZ). The remaining nitrates exist at a persistent concentration without aggregating into bulk-phase AgNO 3 . X-ray absorption spectroscopy results further indicate that iodine adsorption occurs on not just Ag 0 Z but also on AgZ and a portion of the nitrates in the system. AgZ adsorbs a sizable quantity of iodine early in the aging process, but its capacity drops rapidly over time. For well-aged samples, nitrates are responsible for up to 95% of mordenite’s iodine capacity. Overall, these results have enhanced our understanding of the aging process in silver mordenite and are expected to guide the development of superior adsorbents for the capture of radioactive iodine from reprocessing off-gas.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Characterization of Dry-Air Aged Granules of Silver-Functionalized Silica Aerogel

This is a letter report to complete level 3 milestone "Assess aging characteristics of silica aerogels" for DOE FCRD program. Recently, samples of Ag 0 -functionalized silica aerogel were aged in flowing dry air for up to 6 months and then loaded with iodine. This dry-air aging simulated the impact of long-term exposure to process gases during process idling. The 6-month aged sample exhibited an iodine sorption capacity of 32 mass%, which was 9 mass % lower than that for an un-aged Ag 0 -functionalized silica aerogel. In an attempt to understand this decrease in sorption capacity, we characterized physical properties of the aged samples with Brunauer-Emmett-Teller (BET) nitrogen adsorption, X-ray diffraction (XRD), and high resolution scanning electron microscopy (SEM). The results showed no impact of aging on the aerogel microstructure or the silver nanoparticles in the aerogel, including their spatial distribution and morphology.

Aging↗

Preparation of NO 2 -Aged Silver-Functionalized Silica-Aerogel and Silver Mordenite Samples

Reprocessing used nuclear fuel can result in the volatilization of radioactive gaseous species, including 129 I, into the various process off-gas streams. In order to comply with US regulatory requirements, plant off-gas streams must be treated to remove the iodine prior to discharging the off-gas into the environment. The performance of available gas removal methods depends not only on the concentration of the volatile radioisotope of interest, but also on other constituents that could be present in the reprocessing off-gas streams. Some of the constituents, such as NOx produced during fuel dissolution, are known to have deleterious effects on the capture performance of silver-based sorbents used for iodine removal. Commercially available reduced silver mordenite (AgZ) has an iodine saturation concentration of 7.0-9.0 wt%, and its iodine sorption capacity is reduced by 20-50% as a result of NO2 aging. Silverfunctionalized silica aerogel (AgAerogel), an alternative for iodine capture, has an initial iodine saturation of 29.0 wt% and its iodine capacity is only reduced by 15% from NO2 aging. Understanding the differences in aging behavior between AgZ and AgAerogel is critical to determining the behavior of these sorbents under realistic off-gas conditions. To assist in future technical studies on this topic, samples of both AgZ and AgAerogel were aged with NO2. In the experiment, 10.2190 g of AgZ and 10.1771 g of AgAerogel were exposed to a static 0.75% NO 2 /dry air blend for a period of 28 days. The samples were then removed and stored under argon until needed for future experiments.=

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stimuli‐Responsive Emission from Hybrid Metal Halides

Abstract Stimuli‐responsive photoluminescent (PL) materials have attracted considerable attention in recent years owing to their potential applications in anti‐counterfeiting, information encryption, and sensing. Further investigations of the transformation mechanism and potential applications of stimulus‐responsive PL materials are considerably important. In the current study, an organic–inorganic metal halide, C 9 H 15 N 3 SbCl 5 ([C 9 H 13 N 3 ] 2+ is a 1‐(2‐pyridyl) piperazine cation) is obtained, which exhibits a 0D structure withP‐1 space group. At room temperature, when excited by UV light, the C 9 H 15 N 3 SbCl 5 single crystals exhibit unimodal blue light emission at 405 nm, and grinding or hydrostatic pressure induces double‐peak emissions at 405 and 650 nm. Interestingly, double‐emission samples can be restored to single‐emission samples by short annealing or storage in air for 2 weeks, and this process is reversible. Luminescence response to mechanical stimuli can also be achieved in the presence of hydrochloric acid and water. Spectral analysis and the analysis of the microstructural changes revealed that the structural modifications of the inorganic group play a pivotal role in the response to the stimulus. Finally, a composite film device based on C 9 H 15 N 3 SbCl 5 is prepared to demonstrate the potential of these smart materials in anti‐counterfeiting and sensing applications.

Chemistry↗

Infrared Microscopy as a Probe of Composition within a Model Biofuel Cell Electrode Prepared from Trametes versicolor Laccase

Abstract Infrared microscopy was applied in the study of laccase biofuel cell electrodes that demonstrated high current and power densities traceable to the use of a low equivalent weight (EW), short side chain (Aquivion) ionomer in the catalyst layer. The electrodes were prepared from a biocatalyst ink composed of orientation‐directing anthracene‐modified multi‐walled carbon nanotubes (An‐MWCNTs) in a dispersion of ionomer exchanged by hydrophobic cations. The ink was applied to an electronically conductive carbon felt support that was hot‐pressed to a Nafion‐NRE 212 (51 μm thickness) membrane, forming the framework for an air‐breathing biofuel cell cathode. Infrared microscopy sampling was performed with the use of a micro‐attenuated total reflection probe that enabled spectra to be recorded from ∼32 μm diameter circular spatial regions on the materials investigated. Sensitivity to deformation of the soft polymer membrane‐based materials was assessed through trial experiments on pure membrane samples before approaching the compositionally more complex biofuel cell electrodes. In studies of laccase cathodes, infrared spectral features of enzyme, buffer anions and surrounding An‐MWCNTs were identified. Heterogeneity in the spatial distribution of components and unexpected bands traceable to insoluble copper salts were detected. The results suggest directions for improving electrode activity and bring to light needs for advancing quantitative interpretations.

Liang, Ying↗