A Boiloff Calorimetry Test Configuration for the Characterization of Thermal Insulation Systems in Flammable Background Gasses
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Foaming occurs during treatment of high level waste (HLW) at Savannah River Site's Defense Waste Processing Facility (DWPF) in the Chemical Process Cell (CPC) due to high gas generation from process steam and chemical offgas products [1]. The presence of amphiphilic particles in the waste slurry stabilizes the foam [2], [3]. Efficient processing of HLW requires foam control, as foam-overs lead to lower productivity and potential radioactive contamination of condensate streams. DWPF currently employs Siovation Antifoam 747, a surfactant produced by Momentive Performance Materials, as an antifoaming agent during waste treatment. Despite its ability to control foam generation, processing issues have arisen from its use [4]. During DWPF chemical processing, a chemical antifoam agent must be effective at temperatures up to 103 deg. C between pH 3-13. Antifoam 747 is effective at pH 7 but degrades as pH deviates [5]. Antifoam 747 is 90% by weight Momentive{sup TM} L77 and 10% by weight Momentive{sup TM} Y-17580. These ingredients are trisiloxane products, which are especially vulnerable to attack in acidic and caustic environments. Since Antifoam 747 readily degrades, periodic addition is required. Several processing concerns related to Antifoam 747 have affected DWPF operation. Its overuse warranted concern of potential flammable melter offgas under upset conditions due to the generation of carbon dioxide and hydrogen. As a result, a Potential Inadequacy in the Safety Analysis (PISA) was declared [6]. Antifoam contribution has been included in the melter offgas flammability strategy and the quantity of antifoam is monitored to ensure limits are not exceeded. Testing at Savannah River National Laboratory (SRNL) determined that propanal, tri-methylsilanol, and hexamethyldisiloxane are generated as Antifoam 747 degrades, leading to a second PISA [7]. The formation of these byproducts poses additional flammability risks. Furthermore, the methyl and ethyl groups of these compounds may be responsible for the formation of the methyl and ethyl mercury discovered in DWPF [8], [9]. The formation of organomercury has specifically been called out by DOE as a need for increased research. The effectiveness of non-chemical methods for foam control and the efficiency of alternative antifoam agents were evaluated as part of an effort to improve HLW treatment operations at DWPF and to reduce, or eliminate, the flammability hazards associated with Antifoam 747 currently in use. Foaming of high-level waste (HLW) slurries is an issue at the Defense Waste Processing Facility (DWPF) Chemical Process Cell (CPC) which is currently mitigated with a chemical antifoam agent. The effectiveness of non-chemical methods for foam control and the efficiency of alternative antifoams were examined to improve HLW treatment at DWPF and to eliminate the flammability hazards associated with Siovation Antifoam 747 currently in use. Non-chemical foam control methods were deemed unviable for chemical processing at DWPF, as the spray/mist technique requires too much water and space limitations make installation and implementation of headspace agitators unfeasible. The use of ultrasonic energy thickened and further stabilized the foam. Two suitable alternative defoaming agents, Momentive{sup TM} Y- 17112 and Evonik Surfynol{sup R} MD-20, were identified. Both defoamers control foam over a pH range of 4- 13 at boiling, with no flammable degradation products, and only minimal quantities (100-200 mg/kg) are required under glycolic acid conditions. In order to validate the effectiveness of these defoaming agents, SRNL recommends irradiation testing and laboratory scale SRAT/SME experiments with actual radioactive waste. (authors)
Materials flammability data is needed at pressures higher than ever tested before (greater than 10,000 psi). WSTF has designed and is currently building a metals flammability apparatus that can test metals up to 30,000 psi. Solid progress was achieved on the chamber in terms of system build up and fulfilling requirements to perform a NASA Test Readiness Review. Understanding metals flammability data at extreme pressure opens the doors for higher pressure and higher performance oxygen systems. Proposed systems include more reliable/higher performance propulsion systems and more reliable/lighter Environmental Control Life Support Systems (ECLSS). The test system needed for this testing required significant research and development to select a pressurization method and eliminate contact with potentially flammable materials back to the chamber. No additional promoted combustion data was collected in FY21. This International Research & Development (IRAD) proposal was critical to getting the system very close to operational status. This capability is critical to collect forward leaning material flammability data for future spacecraft and ground systems. Forward work has been identified and funding is being sought outside of the Center Innovation Fund (CIF) process for late FY23/FY24.
Low Global Warming Potential (GWP) refrigerants, e.g. Propane (R290) (GWP = 3) and R1234yf (GWP = 4), are becoming a popular choice among refrigeration and HVAC systems, such as vending machines and air conditioning. However, most of Low GWP refrigerants are flammable (ASHRAE class A2 or A3), so safety is a very important consideration when designing and deploying low GWP refrigerants-based equipment in buildings. In the event of a refrigerant leak, the flammability of low GWP refrigerants depends on the local concentration of the refrigerant within the vicinity of the leak. In addition, the low GWP refrigerants concentration is affected by the indoor air environment, such as air flow rate and temperature. In the present study, a computational fluid dynamics (CFD) model is developed to model the flow and temperature of air surrounding a propane-based refrigeration system, as well as the concentration of leaked low GWP refrigerants surrounding the refrigeration system. The model results reveal the concentration distribution of low GWP refrigerants within the building, and as a result, the flammable regions within the building can be identified. Moreover, different ventilation layouts will be tested using the model to improve the design of ventilation. The numerical model can assist in the design of ventilation systems to minimize flammable regions within buildings due to leakage of flammable refrigerants.
The Next Generation Solvent (NGS) is set to replace the Original Caustic Side Solvent Extractant (CSSX) at the Salt Waste Processing Facility (SWPF). The Savannah River National Laboratory (SRNL) was requested by Savannah River Mission Completion (SRMC), formerly Savannah River Remediation (SRR), to perform a literature review on the following topics to address flammability concerns with the current solvent: Isopar ® L vapor pressure curve for NGS, partitioning ratio for the extractant MaxCalix and the modifier Cs-7SB, and high cesium concentration impacts on NGS radiolysis and potential solvent degradation rates in high cesium concentrations. The following conclusions and recommendations are made based on previous experimental work and literature: (1) Current SWPF flammable gas generation calculations use an Isopar ® L vapor pressure curve based on experimental testing with the Original CSSX solvent. No such testing to date has been performed with NGS. It is suggested that the decrease in Cs-7SB concentration for NGS compared to the Original CSSX solvent would lead to a slightly higher vapor pressure at all temperatures in SWPF vessels. A bounding NGS vapor pressure curve has been provided; it is recommended to see if these values would challenge current flammability controls and to perform testing if needed.(2) The partitioning ratio for Cs-7SB is known in the Original CSSX solvent with dilute nitric acid and caustic solutions. No tests could be found for the partitioning of Cs-7SB to dilute boric acid solutions; however, a similar partitioning ratio is expected. Due to the lipophilic alkyl chains on MaxCalix, it is expected to be even less soluble than BOBCalixC6 in the aqueous phase and should not be considered a significant contributor to the f organic term. Additionally, the reaction rate of N,N’,N’’-Tris(3,7-dimethyloctyl)guanidine (TiDG) or its degradation products with a hydrogen radical should be estimated/determined if they are found to be significant contributors to the f organic term. (3) NGS is expected to see much higher Cs concentrations at SWPF in comparison to its use at the Modular CSSX Unit (MCU). These higher Cs concentrations could influence radiolytic degradation rates of the solvent. NGS appears to be fairly stable to radiolytic degradation based on previous testing and its use at MCU. However, there has not been radiolytic flammable gas generation testing with NGS to date. There is a risk that the continued use of G-values obtained for flammable gases produced from the irradiation of the Original CSSX solvent is not bounding for NGS, but this is considered a very low risk due to the similarities in the composition of the solvents, as well as the conservatisms in the experimental design of the Original CSSX testing.
The flammability requirements of the various manned space programs have required development of electronic configurations that would eliminate any flammability hazard to crews or missions. Initial test and development efforts were directed at the development of nonflammable or self-exsinguishing materials. It was soon realized that a more relevant approach in eliminating flammability hazards was to consider materials as to their application and configuration. Design concepts for electronic black boxes and modules were tested in oxygen enriched atmospheres, and it was found that various types of sealed configurations would generally eliminate any flammability hazard. The type of configuration and its construction was found to be of more importance in the elimination of flammability hazards in electronic configurations than the types of materials utilized in them. The design concepts developed for fire hazard free electronic configurations for use in manned space programs of electronic configurations for use in manned space programs are applicable for the design of electronic hardware for any use or environment.
The design of the Skylab missions, 1973 to 1974, was intended to exclude any direct handling of hazardous, toxic, or reactive materials. The materials processing facility and multipurpose furnace provided a contained environment for conducting metals melting, brazing, sphere forming, and crystal growth experiments. At the end of the third mission, following the completion of all other experiments, the materials processing facility was used for a series of flammability experiments. The flammability tests were done last because of the contamination expected from the burning of the materials within the facility. The flammability tests demonstrated a number of peculiar effects that have implications for future design (fire detection, location, and suppression/control). Although the results of the flammability tests contain lessons appropriate to planning, a number of events during the flight illustrate situations or conditions that pose considerations beyond the commonly accepted range of concern for safety-related matters. This presentation includes a discussion of: Skylab flammability studies and the implications for fire suppression/control; false fire alarms and the Skylab fire detection system; space environmental effects on materials that are normally benign; spills/release of contaminants; the detrimental effect that the release of non-hazardous materials have on detection systems; and the problem of locating sources/originating point of hazards.
In order to reduce the risk of decompression sickness associated with spacewalks, NASA is considering designing the next generation of exploration vehicles and habitats with a different cabin environment than used previously. The proposed environment uses a total cabin pressure of 52.7 to 58.6 kPa with an oxygen concentration of 30 to 34% by volume and was chosen with material flammability in mind. Because materials may burn differently under these conditions and there is little information on how this new environment affects the flammability of the materials onboard, it is important to conduct material flammability experiments at the intended exploration atmosphere. One method to evaluate material flammability is by its ease of ignition. To this end, piloted ignition delay tests were conducted in the Forced Ignition and Spread Test (FIST) apparatus subject to this new environment. In these tests, polymethylmethacylate (PMMA) was exposed to a range of oxidizer flow velocities and externally applied heat fluxes. The ultimate goal is to determine the individual effect of pressure and the combined effect of pressure and oxygen concentration on the ignition delay. Tests were conducted for a baseline case of normal pressure and oxygen concentration, low pressure (58.6 kPa) with normal oxygen (21%). Future work will focus on low pressure with 32% oxygen concentration (space exploration atmosphere - SEA) conditions. It was found that reducing the pressure while keeping the oxygen concentration at 21% reduced the ignition time by 17% on average. It was also noted that the critical heat flux for ignition decreases in low-pressure conditions. Because tests conducted in standard atmospheric conditions will underpredict the flammability of materials intended for use on spacecraft, fire safety onboard at exploration atmospheres may be compromised.
A number of future NASA missions involving the exploration of the Moon and Mars will be human-rated and thus require high-specific-energy rechargeable batteries that possess enhanced safety characteristics. Given that Li-ion technology is the most viable rechargeable energy storage device for near-term applications, effort has been devoted to improving the safety characteristics of this system. There is also a strong desire to develop Li-ion batteries with improved safety characteristics for terrestrial applications, most notably for hybrid electric vehicle (HEV) and plug-in hybrid electric vehicle (PHEV) automotive applications. Therefore, extensive effort has been devoted recently to developing non-flammable electrolytes to reduce the flammability of the cells/battery. A number of electrolyte formulations have been developed, including systems that (1) incorporate greater concentrations of the flame-retardant additive (FRA); (2) use di-2,2,2-trifluoroethyl carbonate (DTFEC) as a co-solvent; (3) use 2,2,2- trifluoroethyl methyl carbonate (TFEMC); (4) use mono-fluoroethylene carbonate (FEC) as a co-solvent and/or a replacement for ethylene carbonate in the electrolyte mixture; and (5) utilize vinylene carbonate as a "SEI promoting" electrolyte additive, to build on the favorable results previously obtained. To extend the family of electrolytes developed under previous work, a number of additional electrolyte formulations containing FRAs, most notably triphenyl phosphate (TPP), were investigated and demonstrated in experimental MCMB (mesocarbon micro beads) carbon- LiNi(0.8)Co(0.2)O2 cells. The use of higher concentrations of the FRA is known to reduce the flammability of the electrolyte solution, thus, a concentration range was investigated (i.e., 5 to 20 percent by volume). The desired concentration of the FRA is the highest amount tolerable without adversely affecting the performance in terms of reversibility, ability to operate over a wide temperature range, and the discharge rate capability. The use of fluorinated carbonates, much in the same manner as the incorporation of fluorinated ester-based solvents, was employed to reduce the inherent flammability of mixtures. Thus, electrolyte formulations that embody both approaches are anticipated to have much lower flammability, resulting in enhanced safety.
In aircraft propulsion as well as stationary power generation, gas turbine engines remain a key energy conversion technology due to their high thermal efficiencies and low emissions. However, as emission requirements become increasingly stringent, engine manufacturers have sought to design combustion systems that operate near the fuel-lean limit of flammability. In this study, superadiabatic matrix-stabilized combustion, also known as porous media combustion, is evaluated as an advanced combustion concept for extending the lean flammability limit to achieve improved efficiency and emissions. To this end, a Brayton cycle analysis is developed and key parameters of the porous matrix are identified for maximizing the extension of the lean flammability limit. It is shown that stabilization of combustion below the nominal lean flammability limit allows for the design of engines with significantly higher pressure ratios and lower dilution ratios without increasing turbine inlet temperatures, thus improving cycle thermal efficiency. Combustor flammability limits were shown to be extendable by up to 32% when employing matrix-stabilized combustion, resulting in thermal efficiency gains of up to 11% compared to a nominal design.
The recently introduced hydrofluoroolefin (HFO) refrigerants, including R1234yf and R1234ze(E), have significantly lower global warming potentials (GWPs) than traditional hydrofluorocarbon (HFC) refrigerants like R410A. However, prior tests show that direct drop-in of pure R1234yf or R1234ze(E) into equipment designed for R410A results in a decrease in heat exchanger capacity and the system coefficient of performance. The primary reason is the lower in-tube heat transfer performance of R1234yf and R1234ze(E) compared with that of R410A. To address this issue, previous studies have mixed the mildly flammable HFC R32 with HFOs to improve system performance, with HFC R125 also added to suppress flammability. Previous studies selected compositions based on simple cycle analyses and did not consider modifications of the heat exchanger circuitry configuration to adapt to the new refrigerants. This study presents a novel multi-objective optimization approach to design a refrigerant composition that maximizes energy efficiency within flammability and GWP limits. The approach in this work simultaneously optimizes mixture composition and heat exchanger circuitry configuration. A case study on a rooftop unit indicates that, compared with mixture-only optimization, simultaneous optimization of mixture and heat exchanger circuitry yields a 5.9% improvement in cycle efficiency and a 48.6% reduction in refrigerant flammability with a GWP of 268. Circuitry optimization using refrigerants with different temperature glides shows that the larger the temperature glide is, the larger EER improvement is obtained. The results show that zeotropic blends with a large temperature glide are more sensitive to the refrigerant circuitry than pure refrigerants and may suffer significant performance degradation with subpar heat exchanger circuitry design. The proposed optimization approach is generally applicable to mixtures with any number of components. Using this approach to design a HVAC system can yield higher system efficiency within flammability and GWP constraints.
Material flammability is an important factor in determining the pressure and composition (fraction of oxygen and nitrogen) of the atmosphere in the habitable volume of exploration vehicles and habitats. The method chosen in this work to quantify the flammability of a material is by its ease of ignition. The ignition delay time was defined as the time it takes a combustible material to ignite after it has been exposed to an external heat flux. Previous work in the Forced Ignition and Spread Test (FIST) apparatus has shown that the ignition delay in the currently proposed space exploration atmosphere (approximately 58.6 kPa and32% oxygen concentration) is reduced by 27% compared to the standard atmosphere used in the Space Shuttle and Space Station. In order to determine whether there is a safer environment in terms of material flammability, a series of piloted ignition delay tests using polymethylmethacrylate (PMMA) was conducted in the FIST apparatus to extend the work over a range of possible exploration atmospheres. The exploration atmospheres considered were the normoxic equivalents, i.e. reduced pressure conditions with a constant partial pressure of oxygen. The ignition delay time was seen to decrease as the pressure was reduced along the normoxic curve. The minimum ignition delay observed in the normoxic equivalent environments was nearly 30% lower than in standard atmospheric conditions. The ignition delay in the proposed exploration atmosphere is only slightly larger than this minimum. Interms of material flammability, normoxic environments with a higher pressure relative to the proposed pressure would be desired.
As NASA plans to return people to the Moon for extended durations, we present an experiment concept to understand fire and material flammability there. A small combustion chamber would be used to conduct the first-ever combustion tests on another world. Multiple fuel samples are to be individually burned in Lunar gravity, with cameras and other sensors recording flame characteristics. The main hypothesis is that some materials burning in Lunar-g are more flammable than on Earth. The reason is that buoyant flow has two counteracting effects on material flammability. Increasing gravity level permits more fresh oxygen to be supplied to the flame, but if the buoyant speed is too high, combustion chemistry and increased cooling hinder combustion. This has important implications for the current 1-g material screening method used by NASA. Oxygen limits for upward and downward spread on the Moon will be compared to 1-g values. Earth-based partial gravity facilities (drop towers, aircraft, and sounding rockets) will be used to refine the experiment and provide some limited-duration data. Measured flame characteristics in 1-g and Lunar-g will be compared to a detailed model. These will refine pressure-gravity scaling relations that will then be applied to other g-levels. The work directly addresses knowledge gaps in flammability and crew safety as defined in several NASA strategic documents.
The flammability boundary of a solid is U-shaped with the ordinate as ambient oxygen percentage (or total pressure) and the abscissa represents flow velocity, gravity level, stretch rate, etc. The left side of the flammability boundary is the quenching branch, and the right side is the blow-off branch. Quenching is due to a weak flame whose heat release from combustion cannot overcome the excessive heat losses from, for example, radiation. Blow-off is due to a short gas residence time that is smaller than the chemical reaction time (traditionally referred to as the small Damköhler number effect). For thick solids, the heat conduction into the solid interior has a long transient after ignition before the solid temperature reaches the steady state. During this slow transient, there is excessive (i.e. more than that at the steady state) gas phase heat conduction into the solid interior. From the viewpoint of the quasi-static gaseous flame, this is an additional heat loss that will affect the gas flame's flammability. In this work, a previously developed one-dimensional axisymmetric stagnation-point diffusion flame model is extended to account for the excessive heat loss into the solid beyond the steady burning state. A non-dimensional excessive conductive heat loss parameter Ψ is defined in the paper to account for the transient solid effect. For each Ψ, the gas phase is considered reaching a quasi-steady state. Extensive numerical computations have been performed to determine the extinction boundary and the characteristics of near-limit flames. The U-shaped flammability boundary is now a series of boundaries with Ψ as a parameter. Flame structures under the same environment condition but with different Ψ are compared. For a given oxygen ambient, the extinction boundary Ψ vs stretch rate is an inverted U-shape. The boundary consists of a blowoff branch and a radiative quenching branch. Extensive computed data including flame and pyrolysis temperatures, burning rate, flame standoff distance, species concentration, and reaction rate are presented along the extinction boundaries. Heat balance analysis is performed for both the gas phase and the gas-solid interface. Along the extinction boundary, the relative importance of conduction, convection, radiation, and chemical reaction are analyzed in detail.
(1) Executive Summary: End of life batteries (EOLBs) present a cost and safety liability for their owners and stakeholders. This is due flammability, energy, and power with EOLBs. Current approaches include cumbersome, expensive packaging, specialized shipping, regulated storage, and they are responsible for over half of the cost of recycling. They all expensively and inadequately address symptoms. OnTo has developed and proven a simple way to resolve the problem systemically, through depowering of lithium-ion batteries (and most any battery other than lead). The low-cost process removes flammability, power, and energy in EOLBs through non-toxic chemical processing. The opportunity for commerce of inert scrap is at least $5 billion greater than the commerce in hazardous scrap, all made possible through OnTo’s technology for efficiency and safety. (2) Depowering Improves Safety and Decreases Cost of Battery Ownership: OnTo’s depowering technology will remove half of the cost of EOLB management and recycling. Without this technology, EOLB recycling will always be a liability. EOLB is hazardous due to inherent flammability of electrolyte and lithium. The shipping and commerce of EOLBs is costly and dangerous all along the chain of custody from owner, dealership/shop, shipper, second-life sorter, (shipper again), and finally to the destination facility recycler. OnTo’s depowering service renders inert most any EOLB packs, modules, and cells. The technology uses a brief, non-toxic treatment applicable to most any chemistry. The industry needs a safe, simple, modular, and inexpensive method to render EOLBs as inert scrap. OnTo’s deactivation system is scalable to the needs of any customer along the EOLB chain of custody. (3) Evidence of Successful Depowering: Untreated batteries will catch fire and explode under abuse conditions such as heat or crush. Slide 2 below shows that untreated batteries will blow-up and expel their internal components with heating, after OnTo’s depowering treatment, the same battery is inert with the same heat treatment (Fig. 7 in the slide). Depowering also removes electrolyte reactivity, eliminating the production of HF and other toxins (Fig 6. in the slide) The depowering process is applicable to large, 26 Ah cells. Fig. 5 in the slide shows the removal of all the electrolyte from whole cells. Removal of flammable material from an EOLB contributes to the inert behavior. OnTo developed this technology through a project supported by the US Department of Energy EERE program, with partners including Seattle King County Metro Transit. While OnTo has generated evidence of successful depowering of batteries, in 2020, a follow-on voucher opportunity for third party analysis of depowered cells and materials was approved through CalTestBed. The expertise of the battery and materials research groups at Lawrence Berkeley National Laboratory will characterize these depowered cells to provide better understanding of the materials level changes in depowering. (4) Pilot Plant for Depowering EOLBs: Making the spoke work in hub-and-spoke While other companies are marketing the hub-and-spoke approach for recycling EOLBs, they rely on dangerous, expensive shredding methods with flimsy IP protection. OnTo offers the only patented, proven ability to depower EOLBs from most any chemistry – at half of the capital cost required for shredding, while eliminating the liability, danger, and waste streams inherent with shredding. The proposed commercial pilot facility is (5) OnTo Technology LLC Company: OnTo develops advanced battery recycling innovations that produce manufacturing quality electrode materials from recycled batteries. Their patented Cathode-healing™ and Deactivation/Depowering processes improve safety and reduce the cost of recycling. OnTo’s breakthrough technologies produce advanced materials for manufacturing batteries useful in applications from portable power to electric vehicles. Contact: Steve Sloop OnTo Technology LLC, 63221 Service Road, STE F, Bend, OR 97703, ssloop@onto-technology.com , 541-389-7897
The effect of changes in the input parameters (air leakage flow rate and temperature and lubricating oil inlet flow rate and temperature) over a specified range on the flammability conditions within an aircraft engine bearing sump was investigated. An analytical study was performed to determine the effect of various parameters on the generation rate of oil vapor from oil droplets in a hot air stream flowing in a cylindrical tube. The ignition of the vapor-air mixture by an ignition source was considered. The experimental investigation demonstrated that fires would be ignited by a spark ignitor over the full range of air and oil flow rates and air temperatures evaluated. However, no fires could be ignited when the oil inlet temperature was maintained below 41.7 K (290 F). The severity of the fires ignited were found to be directly proportional to the hot air flow rate. Reasonably good correlation was found between the mixture temperature in the sump at the ignitor location and the flammability limits as defined by flammability theory; thus a fairly reliable experimental method of determining flammable conditions within a sump was demonstrated. The computerized mathematical model shows that oil droplet size and air temperature have the greatest influence on the generation rate of oil vapor.
The thermochemical and flammability properties of some thermally stable polymers considered for use in aircraft interiors are described. The properties studied include: (1) thermomechanical properties such as glass transition and melt temperature; (2) dynamic thermogravimetric analysis in anaerobic environment; (3) flammability properties such as oxygen index, flame spread, and smoke evolution; and (4) selected physical properties. The thermoplastic polymers evaluated include polyphenylene sulfide, polyaryl sulfone, 9,9-bis(4-hydroxyphenyl)-fluorene polycarbonate-poly(dimethylsiloxane) and polyether sulfone. The thermoset polymers evaluated include epoxy, bismaleimide, a modified phenolic, and polyaromatic melamine resin. These resins were primarily used in the fabrication of glass-reinforced prepregs for the construction of experimental panels. Test results and relative rankings of some of the flammability parameters are presented, and the relationship of the molecular structure, char yield, and flammability properties of these polymers are discussed.