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At least 433 records · Page 24

In‐Process Melt Separation of PE/PET Blends for Upcycling via Twin‐Screw Extrusion. Impact of Catalyst Reagents on PET Depolymerization

Part 1 of this work focused on depolymerizing polyethylene terephthalate (PET) in twin-screw extrusion, as part of a broader project to continuously separate PET from polyolefins in the melt. This study focused on linear low-density polyethylene (LLDPE) and PET films and the use of ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), and bis(2-hydroxyethyl) terephthalate (BHET) to depolymerize the PET in the extruder to levels above 90% Mw. In part 2, the focus will shift to achieving separation of the two polymers in the twin-screw extruder, which is made possible due to a 90% reduction in the Mw of the PET, which caused a decrease of its viscosity by several orders of magnitude. Owing to the viscosity difference and pressure buildup in the die, the low-viscosity PET preferentially exited a degassing vent instead of going through the die. This is because the flow of the PET would travel through a non-pressure vent rather than through a high-pressure die. However, owing to the higher viscosity of the LLDPE, the pressure was too high to pass through such a small diameter vent hole. Supercritical CO₂ (SCCO₂) was used to assist in this extraction, but SCCO₂ negatively impacted the overall degree of separation. Through analysis of the separated materials, it was concluded that a very high separation of the two materials was achieved. TGA and FTIR confirmed that the material separated from the vent was 100% PET. The material removed from the die was composed of 90% LLDPE and 10% PET.

36 MATERIALS SCIENCE↗

Modeling delayed thermal runaway in nitric acid-soaked cat litter mixed with radioactive waste

Thermal ignition of radioactive waste within a 55-gallon drum was simulated by using a pressure-dependent waste decomposition model (Hobbs et al. in Process Saf Environ Prot https://doi.org/10.1016/j.psep.2022.09.047, 2022) calibrated with data from full-scale drum experiments (Parker et al. in The thermolytic response of a surrogate RNS waste mixture at the drum scale. Los Alamos National Laboratory Report LA-UR-16-21760, 2016) and validated with experiments from multiple laboratories (Hobbs et al. in Thermal analysis of aged nitric acid-soaked kitty litter in TRU waste drums-23370.WM2023 Conference, Phoenix, AZ, 2023). The acceleration of nitric acid chemistry reacting with an organic cat litter leading to thermal ignition was likely triggered by a restricted vent in the drum. Here, we address whether the form of the rate equation in (Hobbs et al. in Process Saf Environ Prot https://doi.org/10.1016/j.psep.2022.09.047, 2022) is sufficient to extrapolate thermal ignition within aged drums of similar content that have been stored in Texas for over nine years by investigating four different reaction rate forms for waste decomposition. A critical reaction rate reduction analysis is performed on each of these models to determine if delayed thermal runaway within vented aged waste is possible after nine years. We found that a pressure-dependent first-order rate expression not only predicted the accidental ignition of the waste drum, but the form also matches multiple experiments from different laboratories. Even though the waste composition decreases over time, the model predicts that acceleration leading to thermal runaway is possible if the waste is confined, even after 9 years. In conclusion, waste containing oxidizers such as nitric acid should not be mixed with organic adsorbents, especially if the waste is confined.

cookoff↗

Achieving superior carbon transfer efficiency and pH control using membrane carbonation with a wide range of CO 2 contents for the coccolithophore Emiliania huxleyi

The economic viability of microalgal-derived products relies on rapid CO 2 transfer in a cost-effective manner. Many industrial gas streams contain concentrated CO 2 that, if converted to useful products, would lower greenhouse gas emissions and valorize the wasted CO 2 . Membrane carbonation (MC) uses non-porous hollow-fiber gas-transfer membranes to deliver CO 2 without bubble formation, which makes it possible to achieve a high carbon-transfer efficiency (CTE). However, inert gasses in the industrial streams (e.g., N 2 , O 2 , and H 2 O) can significantly lower the CO 2 -delivery rate. The means to overcome the buildup of inert gases in the membrane lumen is to manage the distal end of the membranes to sweep out inert gases while not wasting significant CO 2 . A MC-venting strategy was evaluated for CO 2 inputs from 5% to 100%. Abiotic tests using a restricted exit flow could achieve >95% CTE abiotic for industrial CO 2 streams. When integrated with semi-continuous cultivation of a marine coccolithophore, Emiliania huxleyi , CO 2 delivery and venting were on-demand based on a pH set points and pH-actuated feed and venting valves. MC using the venting strategy achieved 100% CTE biotic when delivering 100% and 50% CO 2 , which was better than 50% CTE biotic obtained from pH-controlled sparging of 100% CO 2 -sparging. E. huxleyi consistently fixed ~80% of the delivered CO 2 into biomass, and the remaining ~20% to calcite coccoliths. Finally, the compact size of MC modules, stable pH control, and no shear forces from bubble agitation during the CO 2 delivery made MC an ideal match for cultivation of coccolithophores, which are sensitive to shear forces and pH fluctuations.

54 ENVIRONMENTAL SCIENCES↗

Gas Generation Models for Thermal Runaway in Lithium Ion Batteries

A numerical model is implemented to study cell venting, internal pressure, and gas-phase dynamics behavior of Li-ion cells undergoing thermal runaway. A k-ɛ Reynolds-Averaged Navier-Stokes (RANS) model is adopted to describe the turbulent flow out of the cells, while the fluid dynamics inside the cells is described by Darcy-Forchheimer’s equation. Thermal abuse reactions and gas generation kinetics are described by a single-step lumped reaction model. A series of computational fluid dynamics (CFD) simulations are conducted on a single cell at various states-of-charge (100%, 50%, 25%) to demonstrate detailed flow and thermal behavior as a function of quantity of gas generated during cell venting. Venting events are categorized into two stages: i) breaching of the cell container and ii) thermal runaway reactions. It is shown that the cell response is dominated by the second stage since most of the gases are generated during thermal runaway. Also, the propensity for propagation is highly affected by state-of-charge (SOC). Cells at higher SOCs produce more heat and gas during the venting event, owing to higher mass and concentrations of reacting gases, and consequently reach higher internal cell pressures which increase the risk of side-wall breaching.

Kim, Jinyong↗

Thermal/structural optimization of cryogenic storage systems.

An analytical method has been developed to optimize a cryogenic storage system designed for long term storage of cryogenic propellants. The type of propellant, mission duration, thermal environment, insulation thermal properties, insulation vent time, and the storage system weight penalty imposed by the design pressure were considered as the dependent parameters. The optimum system insulation thickness and vent pressure were then calculated in terms of these parameters. The method was applied to the design of the Space Shuttle Orbiter oxygen and hydrogen tanks to obtain an optimum design. It was determined that for the mission examined, the hydrogen tank optimum design was close to the initial pressure. A continuously vented hydrogen tank, therefore, was close to the optimum design. Also, it was determined that for this particular mission the oxygen tank should not be vented.

Navickas, J.↗

Centaur Propellant Thermal Conditioning Study

A wicking investigation revealed that passive thermal conditioning was feasible and provided considerable weight advantage over active systems using throttled vent fluid in a Centaur D-1s launch vehicle. Experimental wicking correlations were obtained using empirical revisions to the analytical flow model. Thermal subcoolers were evaluated parametrically as a function of tank pressure and NPSP. Results showed that the RL10 category I engine was the best candidate for boost pump replacement and the option showing the lowest weight penalty employed passively cooled acquisition devices, thermal subcoolers, dry ducts between burns and pumping of subcooler coolant back into the tank. A mixing correlation was identified for sizing the thermodynamic vent system mixer. Worst case mixing requirements were determined by surveying Centaur D-1T, D-1S, IUS, and space tug vehicles. Vent system sizing was based upon worst case requirements. Thermodynamic vent system/mixer weights were determined for each vehicle.

Blatt, M. H.↗

The mineralogy and the isotopic composition of sulfur in hydrothermal sulfide/sulfate deposits on the East Pacific Rise, 21 deg N latitude

The mineralogy and isotopic composition of sulfur found in hydrothermal deposits associated with five groups of vents along the ridge axis of the East Pacific Rise near 21 deg N latitude are investigated. Solid samples of mixed sulfides and sulfates from mounds, chimneys and the surrounding sediment as well as fresh basaltic glass were examined with a portable X-ray fluorescence spectrometer and by scanning electron microscopy, X-ray diffractometry, and electron microprobe analysis. For the three vents of exit temperature close to 350 C, the chimneys are found to be rich in copper sulfides, while for those of temperatures around 300 C, zinc sulfide is found to predominate. The major sulfides found in the chimneys include wurtzite, chalcopyrite, pyrite and cubanite, with anhydrite the dominant sulfate. Significant mineralogical differences are found between active and inactive vents. The isotopic composition of sulfur in anhydrites from active vents is observed to be close to that of sea water and consistent with a derivation from sea water sulfate. The isotopic composition of sulfur in the sulfide minerals is explained in terms of precipitation from solutions with reduced sulfur derived from basalts or basaltic magmas, and sea water sulfate. Finally, the deposits are interpreted as the results of the mixing of H2S-dominated hydrothermal fluids with cold sea water near the sea floor.

Styrt, M. M.↗

Liquid/Gas Vortex Separator

Liquid/gas separator vents gas from tank of liquid that contains gas randomly distributed in bubbles. Centrifugal force separates liquid and gas, forcing liquid out of vortex tube through venturi tube. Gas vented through exhaust port. When liquid detected in vent tube, exhaust port closed, and liquid/gas mixture in vent tube drawn back into tank through venturi.

Morris, B. G.↗

Submarine hot springs and the origin of life

The popular hypothesis that life originally arose in hydrothermal vents at oceanic ridge crests is examined. It is shown that the high temperatures in the vents would not allow synthesis of organic compounds, but would decompose them, unless the exposure time at vent temperature was short. Even if the essential organic molecules were available in the hot hydrothermal waters, the subsequent steps of polymerization and the conversion of these polymers into the first organisms would not occur as the vent waters were quenched to the colder temperatures of the primitive oceans.

Miller, Stanley L.↗

Independent Orbiter Assessment (IOA): Analysis of the atmospheric revitalization pressure control subsystem

The results of the Independent Orbiter Assessment (IOA) of the Failure Modes and Effects Analysis/Critical Items List (FMEA/CIL) are presented. The IOA approach features a top-down analysis of the hardware to determine failure modes, criticality, and potential critical items. To preserve independence, this analysis was accomplished without reliance upon the results contained within the NASA FMEA/CIL documentation. The independent analysis results corresponding to the Orbiter Atmospheric Revitalization and Pressure Control Subsystem (ARPCS) are documented. The ARPCS hardware was categorized into the following subdivisions: (1) Atmospheric Make-up and Control (including the Auxiliary Oxygen Assembly, Oxygen Assembly, and Nitrogen Assembly); and (2) Atmospheric Vent and Control (including the Positive Relief Vent Assembly, Negative Relief Vent Assembly, and Cabin Vent Assembly). The IOA analysis process utilized available ARPCS hardware drawings and schematics for defining hardware assemblies, components, and hardware items. Each level of hardware was evaluated and analyzed for possible failure modes and effects. Criticality was assigned based upon the severity of the effect for each failure mode.

Saiidi, M. J.↗

Chemical environments of submarine hydrothermal systems

Perhaps because black-smoker chimneys make tremendous subjects for magazine covers, the proposal that submarine hydrothermal systems were involved in the origin of life has caused many investigators to focus on the eye-catching hydrothermal vents. In much the same way that tourists rush to watch the spectacular eruptions of Old Faithful geyser with little regard for the hydrology of the Yellowstone basin, attention is focused on the spectacular, high-temperature hydrothermal vents to the near exclusion of the enormous underlying hydrothermal systems. Nevertheless, the magnitude and complexity of geologic structures, heat flow, and hydrologic parameters which characterize the geyser basins at Yellowstone also characterize submarine hydrothermal systems. However, in the submarine systems the scale can be considerably more vast. Like Old Faithful, submarine hydrothermal vents have a spectacular quality, but they are only one fascinating aspect of enormous geologic systems operating at seafloor spreading centers throughout all of the ocean basins. A critical study of the possible role of hydrothermal processes in the origin of life should include the full spectrum of probable environments. The goals of this chapter are to synthesize diverse information about the inorganic geochemistry of submarine hydrothermal systems, assemble a description of the fundamental physical and chemical attributes of these systems, and consider the implications of high-temperature, fluid-driven processes for organic synthesis. Information about submarine hydrothermal systems comes from many directions. Measurements made directly on venting fluids provide useful, but remarkably limited, clues about processes operating at depth. The oceanic crust has been drilled to approximately 2.0 km depth providing many other pieces of information, but drilling technology has not allowed the bore holes and core samples to reach the maximum depths to which aqueous fluids circulate in oceanic crust. Such determinations rely on studies of pieces of deep oceanic crust uplifted by tectonic forces such as along the Southwest Indian Ridge, or more complete sections of oceanic crust called ophiolite sequences which are presently exposed on continents owing to tectonic emplacement. Much of what is thought to happen in submarine hydrothermal systems is inferred from studies of ophiolite sequences, and especially from the better-exposed ophiolites in Oman, Cyprus and North America. The focus of much that follows is on a few general features: pressure, temperature, oxidation states, fluid composition and mineral alteration, because these features will control whether organic synthesis can occur in hydrothermal systems.

Shock, Everett L.↗

Lava flow-field morphological classification and interpretation: Examples from Venus

Recent analyses suggest that thermal constraints will act to limit the maximum length of an advancing lava flow being fed at a given volume or mass effusion rate from a vent. These constraints can be characterized through the Gratz number, which has a large value at the vent and decreases down flow; under a wide range of conditions, motion apparently ceases when the Gratz number has decreased to a value close to 300. In cooling-limited flows, effusion from the vent should be steady; the flow front thickens, eventually stops due to this cooling, and the central channel does not drain. If the vent remains active, a break-out flow will form from some point on the margin of the initial flow unit. If flows on planetary surfaces can be shown to be cooling limited, eruption rates can be estimated. In this analysis, we illustrate the morphological characteristics of various flow configurations, and we describe the application of these concepts to a flow length histogram for a hypothetical flow field and then apply this to an example on Venus.

Head, J. W.↗

Crystallization history of the 1984 Mauna Loa lava flow

During a 3-week eruption in 1984, Mauna Loa produced vent lavas that increased in crystallinity from less than 1 to 30%, and 27-km-long flows that increased in crystallinity as they moved downstream. We examined the crystallization history of these lavas using crystal size distribution (CSD) analysis to study the rates of crystallization, viscosity increase, and latent heating. Typical average growth and nucleation rates were 5 x 10(exp -9) cm/s and 5/cu cm/s for microphenocrysts (20- to 500-micron size crystals nucleated in the rift zone) and 5 x 10(exp -8) cm/s and 5 x 10(exp 4)/cu cm/s for microlites (1- to 20-micron size crystals nucleated in the channel). These crystallization rates are high compared with those found in other CSD studies of igneous rocks, probably due to highly nonequilibrium conditions brought on by rapid degassing in the rift zone and cooling in the lava channel. Growth and nucleation rates decreased with time at the vent and with distance downstream. The maximum downstream total crystallinity measured is 39% (25% microlites, 14% microphenocrysts) in a quenched sample 14 km from the vent. Growth and nucleation rates cannot be calculated for postemplacement samples, but they place upper limits of 53-58% on the amount of crystallization in the channel 9-20 km from the vent. Crystallization could have been mostly responsible for the 10(exp 5)-fold downstream increase in apparent viscosity, although degassing and increasing incorporation of solid lava fragments also contributed. Another effect of crystallization on the lava flow was the sizeable latent heating (0.01 J/g/s over the first half of the flow length, if the crystallinity of downstream quench samples is representative of the hot fluid core), which may have been counteracted by entrainment of cooler material. Measurements of crystallization are shown to be crucial in the study of lava flow emplacement dynamics.

Crisp, Joe↗

Effect of pressure on a burning solid in low-gravity

Venting, or depressurization, has been discussed as a possible technique for extinguishing fires on aircraft and spacecraft. Fire suppression plans for the International Space Station Alpha (ISSA) discuss the use of depressurization as a method for extinguishing fires. In the case of an uncontrollable fire, the affected compartment would be vented from an initial pressure of 1.0 atm (14.7 psia) to a final pressure 0.33 atm (4.8 psia) within 10 minutes. However, the lack of low pressure flammability data for solid materials in a low-gravity environment presents an uncertainty for the use of the venting technique. There are also transient effects that need to be considered. It is possible that the flows induced by the venting could intensify the fire. This occurred during flammability tests conducted on board Skylab. In addition, the extinction pressure could be a function of the depressurization rate. Studies conducted with solid propellants have shown that if the pressure is reduced quickly enough, the pressure at extinction will be greater than the steady-state extinction limit. This project, which was started in 1992, is examining both the quasi steady-state and transient effects of pressure reduction on a burning solid in low-gravity. This research will provide low-g extinguishment data upon which policies and practices can be formulated for fire safety in orbiting spacecraft.

Goldmeer, Jeffrey S.↗

Sulfur, Chlorine, and Flourine Degassing and Atmospheric Loading by the 1783 - 1784 AD Laki (Skaftar Fires) Eruption in Iceland

The 1783-1784 Laki tholeiitic basalt fissure eruption in Iceland was one of the greatest atmospheric pollution events of the past 250 years, with widespread effects in the northern hemisphere. The degassing history and volatile budget of this event are determined by measurements of pre-eruption and residual contents of sulfur, chlorine, and fluorine in the products of all phases of the eruption. In fissure eruptions such as Laki, degassing occurs in two stages: by explosive activity or lava fountaining at the vents, and from the lava as it flows away from the vents. Using the measured sulfur concentrations in glass inclusions in phenocrysts and in groundmass glasses of quenched eruption products, we calculate that the total accumulative atmospheric mass loading of sulfur dioxide was 122 Mt over a period of 8 months. This volatile release is sufficient to have generated approximately 250 Mt of H2SO4 aerosols, an amount which agrees with an independent estimate of the Laki aerosol yield based on atmospheric turbidity measurements. Most of this volatile mass (approximately 60 wt.%) was released during the first 1.5 months of activity. The measured chlorine and fluorine concentrations in the samples indicate that the atmospheric loading of hydrochloric acid and hydrofluoric acid was approximately 7.0 and 15.0 Mt, respectively. Furthermore, approximately 75% of the volatile mass dissolved by the Laki magma was released at the vents and carried by eruption columns to altitudes between 6 and 13 km. The high degree of degassing at the vents is attributed to development of a separated two-phase flow in the upper magma conduit, and implies that high-discharge basaltic eruptions such as Laki are able to loft huge quantities of gas to altitudes where the resulting aerosols can reside for months, or even 1-2 years. The atmospheric volatile contribution due to subsequent degassing of the Laki lava flow is only 18 wt.% of the total dissolved in the magma, and these emissions were confined to the lowest regions of the troposhere and therefore important only over Iceland. This study indicates that determination of the amount of sulfur degassed from the Laki magma batch by measurements of sulfur in the volcanic products (the petrologic method) yields a result which is sufficient to account for the mass of aerosols estimated by other methods.

Thordarson, T.↗

Preventing Damaging Pressure Gradients at the Walls of an Inflatable Space System

An inflatable structural system to deploy a space system such as a solar shield, an antenna or another similar instrument, requires a stiffening element after it is extended by the inflated gas pressure. The stiffening element has to be packaged in a folded configuration before the deployment. It must be relatively small, lightweight, non-damaging to the inflated system, and be able to become stiff in a short time. One stiffening method is to use a flexible material inserted in the deployable system, which, upon a temperature curing, can become stiff and is capable to support the entire structure. There are two conditions during the space operations when the inflated volume could be damaged: during the transonic region of the launch phase and when the curing of the rigidizing element occurs. In both cases, an excess of pressure within the volume containing the rigid element could burst the walls of the low-pressure gas inflated portion of the system. This paper investigates those two conditions and indicates the vents, which will prevent those damaging overpressures. Vent openings at the non-inflated volumes have been calculated for the conditions existing during the launch. Those vents allow the initially folded volume to exhaust the trapped atmospheric gas at approximately the same rate as the ambient pressure drops. That will prevent pressure gradients across the container walls which otherwise could be as high as 14.7 psi. The other condition occurring during the curing of the stiffening element has been investigated. This has required the testing of the element to obtain the gas generation during the curing and the transformation from a pliable material to a rigid one. The tested material is a composite graphite/epoxy weave. The outgassing of the uncured sample at 121C was carried with the Cahn Microbalance and with other outgassing facilities including the micro-CVCM ASTM E-595 facility. The tests provided the mass of gas evolved during the test. That data, including the chemical nature of the evolved gas, provided the data for the calculation of the pressure produced within the volume. The evaluation of the areas of the vents that would prevent excessive pressures and provide a rapid release of the gas away from contamination sensitive surfaces has been carried out. The pressure decay with time has been indicated.

Scialdone, John J.↗

Preventing Damaging Pressure Gradients at the Walls of an Inflatable Space System

An inflatable structural system to deploy a space system such as a solar shield, an antenna or another similar instrument requires a stiffening element after it is extended by the inflated gas pressure. The stiffening element has to be packaged in folded configuration before the deployment. It must be relatively small, lightweight, non-damaging to the inflated system and be able to become stiff in a short time. One stiffening method is to use a flexible material inserted in the deployable system, which, upon a temperature curing, can become stiff and is capable of supporting the entire structure. There are two conditions during the space operations when the inflated volume could be damaged: during the transonic region of the launch phase and when the curing of the rigidizing element occurs. In both cases, an excess of pressure within the volume containing the rigid element could burst the walls of the low-pressure gas inflated portion of the system. This paper investigates those two conditions and indicates the vents, which will prevent those damaging overpressures. Vent openings at the non-inflated volumes have been calculated for the conditions existing during the launch. Those vents allow the initially folded volume to exhaust the trapped atmospheric gas at approximately the same rate as the ambient pressure drops. That will prevent pressure gradients across the container walls which otherwise could be as high as 14.7 psi. The other condition occurring during the curing of the stiffening element has been investigated. This has required the testing of the element to obtain the gas generation during the curing and the transformation from a pliable material to a rigid on The tested material is a composite graphite/epoxy weave. The outgassing of the uncured sample at 121 deg Celcius was carried with the Cahn Microbalance and with other outgassing facilities including the micro-CVCM ASTM E-595 facility. The test provided the mass of gas evolved during the test. That data, including the chemical nature of the evolved gas, provided the data for the calculation of the pressure produced within the volume. The evaluation of the areas of the vents that would prevent excessive pressures and provide a rapid release of the gas away from contamination sensitive surfaces has be carried out. The pressure decay with time has been indicated.

Scialdone, John J.↗

Modeling and Test Data Analysis of a Tank Rapid Chill and Fill System for the Advanced Shuttle Upper Stage (ASUS) Concept

The Advanced Shuttle Upper Stage (ASUS) concept addresses safety concerns associated .with cryogenic stages by launching empty, and filling on ascent. The ASUS employs a rapid chill and fill concept. A spray bar is used to completely chill the tank before fill, allowing the vent valve to be closed during the fill process. The first tests of this concept, using a flight size (not flight weight) tank. were conducted at Marshall Space Flight Center (MSFC) during the summer of 2000. The objectives of the testing were to: 1) demonstrate that a flight size tank could be filled in roughly 5 minutes to accommodate the shuttle ascent window, and 2) demonstrate a no-vent fill of the tank. A total of 12 tests were conducted. Models of the test facility fill and vent systems, as well as the tank, were constructed. The objective of achieving tank fill in 5 minutes was met during the test series. However, liquid began to accumulate in the tank before it was chilled. Since the tank was not chilled until the end of each test, vent valve closure during fill was not possible. Even though the chill and fill process did not occur as expected, reasonable model correlation with the test data was achieved.

Flachbart, Robin↗