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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Light Duty Engine Performance Characteristics with Dimethyl Ether and Propane

Here, this paper explores the performance characteristics of a compression ignition HYUNDAI 2.2L engine operating with Dimethyl Ether (DME). Test are carried out at three operating conditions that weigh heavily in the FTP75 certification cycle (1000rpm-12Nm, 1500rpm-50Nm, 2000rpm-100Nm). The engine features a high-pressure common rail fuel injection system designed to operate with liquified gases. The main component of the fuel system is a high-pressure pump that incorporates an electronic inlet metering valve commanded on a crank-angle base to control the rail pressure. The pump, which requires no pressure regulator, provides the flow needed to the injectors without flow returning to the inlet. This novel fueling system is leveraged in tests that are conducted to examine the impact of EGR, combustion phasing, injection pressure on efficiency and emissions. In addition, the impact of introducing 15% Propane by mass is examined. During the tests, the engine ECU is aided by an Engine Controller High Speed Oversight unit (ECHO) to provide combustion phasing control, improved cylinder-to-cylinder uniformity, and an effective optimization over the testing effort. The use of DME and Propane allowed for peak thermal efficiency of nearly 43%. These fuels enable significant carbon index (CI) reductions over the baseline Diesel fuel, with indications that 50% reduction in CO 2 over the Diesel engine are possible.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2023

Role of Intra-Domain Heterogeneity on Ion and Polymer Dynamics in Block Polymer Electrolytes: An Approach for Spatially Resolving Dynamics and Ion Transport

The design of safe and high-performance, nanostructured, block polymer (BP) electrolytes for lithium-ion batteries requires a thorough understanding of the key parameters that govern local structure and dynamics. Yet, the interfaces between microphase separated domains can introduce complexities in this local behavior that can be challenging to quantify. Herein, the local polymer, cation (Li + ), and anion dynamics were described in salt-doped polystyrene block poly(oligo-oxyethylene methyl ether methacrylate) (PS-b-POEM) through a quantitative framework that considered the effects of polymer architecture, segmental mixing, chain stretching, and confinement on polymer mobility and ion transport. This framework was validated through nuclear magnetic resonance (NMR) spectroscopy measurements on solid (dry) polymer electrolyte samples. Notably, a mobility transition temperature (T mobility ) was identified through NMR spectroscopy that captured the local dynamics more accurately than the thermal glass transition temperature. Additionally, the approach quantitatively described the mobility gradient across a domain when segmental mixing effects were combined with chain stretching and confinement information, especially at higher segregation strengths – facilitating the assessment of local ion diffusion and conductivity. As a result, spatially averaged local ion diffusion predictions quantitatively matched NMR-measured ion diffusivities in the BP samples, while spatially summed ionic conductivity predictions across a domain qualitatively captured trends in the measured ionic conductivities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Study on ammonia and dimethyl ether oxidation and kinetic interaction up to 100 atm

NH 3 and DME dual fuel oxidation and kinetic coupling are experimentally studied by using a supercritical pressure jet-stirred reactor (SP-JSR) at 20 and 100 atm, over a temperature range of 500–900 K, and at fuel-lean and stoichiometric conditions with NH 3 to DME molar ratios of 4 and 0.62, respectively. An HP-Mech model for high-pressure NH3/DME oxidation is developed based on our previous studies and it shows generally better performance than other models in the literature on high-pressure oxidation experiments. Due to DME’s strong low-temperature reactivity, it dramatically enhances the oxidation of NH3 at low temperature. However, the effect of NH 3 on DME oxidation varies with temperature. At low temperatures, NH 3 inhibits low-temperature reactivity by consuming OH radicals. In addition, the NH 2 and NO x formation from NH 3 further suppresses the low-temperature DME reactivity by reducing alkylperoxyl and O 2 QOOH radicals via RO 2 + NH 2 = RO + H 2 NO, RO 2 + NO = RO + NO 2 and O 2 QOOH + NO = 2CH 2 O + HO 2 + NO 2 . At intermediate temperatures, due to enhanced kinetic coupling of NH 2 /NO x /HO 2 chemistry, DME oxidation is significantly promoted. It is found that there are two major NH 2 /NO x /HO 2 coupling pathways for OH radical production brought by NH 3 : (1) NH 2 + HO 2 = H 2 NO + OH and (2) NH 2 + NO 2 = H 2 NO + NO with NO + HO 2 = OH + NO 2 . Moreover, the resulting H 2 NO will further contribute to OH production via the H 2 NO/NO x /HONO coupling pathways: H 2 NO + NO 2 = HNO + HONO, HNO + NO 2 = HONO + NO, and HONO (+M) = OH + NO (+M). These new NH 2 /NO x /HO 2 and H 2 NO/NO x /HONO pathways play a critical role in promoting DME oxidation at intermediate temperatures. Novelty and Significance Statement: Blending NH 3 with DME can significantly enhance the reactivity of NH 3 and facilitate its practical application in advanced internal combustion engines. NH 3 /DME oxidation is studied in a novel supercritical pressure jet-stirred reactor up to 100 atm, a much higher pressure than previous studies. An interesting non-monotonic effect of NH3 addition on fuel oxidation has been found. Unique kinetic couplings of NH2/HO2/NOx and H2NO/NOx/HONO brough by NH3 and DME blending are identified to play important roles in radical generation and reactivity promotion. The valuable experimental data and key kinetics revealed in the current work can tremendously improve our understanding of NH 3 /DME oxidation via NO x /RO 2 and NH 2 / H 2 NO/HO 2 /NO x kinetic couplings at low to intermediate temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Disulfonated Poly(arylene ether sulfone) Random Copolymers Containing Hierarchical Iptycene Units for Proton Exchange Membranes

Two series of disulfonated iptycene-based poly(arylene ether sulfone) random copolymers, i.e., TRP-BP (triptycene-based) and PENT-BP (pentiptycene-based), were synthesized via condensation polymerization from disulfonated monomer and comonomers to prepare proton exchange membranes (PEMs) for potential applications in electrochemical devices such as fuel cell. To investigate the effect of iptycene units on membrane performance, these copolymers were systematically varied in composition (i.e., iptycene content) and the degree of sulfonation (i.e., 30–50%), which were characterized comprehensively in terms of water uptake, swelling ratio, oxidative stability, thermal and mechanical properties, and proton conductivity at various temperatures. Comparing to copolymers without iptycene units, TRP-BP and PENT-BP ionomers showed greatly enhanced thermal and oxidative stabilities due to strong intra- and inter-molecular supramolecular interactions induced by hierarchical iptycene units. In addition, the introduction of iptycene units in general provides PEMs with exceptional dimensional stability of low volume swelling ratio at high water uptakes, which is ascribed to the supramolecularly interlocked structure as well as high fractional free volume of iptycene-based polymers. It is demonstrated that the combination of high proton conductivity and good membrane dimension stability is the result of the synergistic effects of multiple factors including free volume (iptycene content), sulfonation degree, hydrophobicity, and swelling behavior (supramolecular interactions).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Exploring Fluoropyridine Electrolytes in Li–S Batteries: Balancing Performance and Stability across Temperatures

A novel high-donor 3-fluoropyridine (3FPy) electrolyte has been introduced for use in Li-S batteries, demonstrating an inhibition effect on the polysulfide shuttle, even without the addition of LiNO 3 . In this study, fluoropyridine electrolytes, including 2-fluoropyridine (2FPy) and 3FPy electrolytes, are studied using electrochemical analysis, mass spectrometry (MS), and high-performance liquid chromatography (HPLC) methods. Collision-induced dissociation spectra revealed that Li + preferentially solvates with different fluoropyridines, with 2FPy exhibiting a stronger interaction due to ortho-fluorine's influence, compared to 4FPy and 3FPy. However, MS and HPLC analyses showed that 2FPy is reactive with polysulfides, while 3FPy offers high solubility for polysulfides and sulfur without reacting with them at room temperature. Further, despite 3FPy performing well at room temperature, further electrochemistry studies at elevated (60 °C) and reduced (0 °C) temperatures reveal the challenges. At high temperatures, LiNO 3 is essential to suppress the polysulfide shuttle; and at low temperatures, the performance with the 3FPy electrolyte significantly lags behind that of the ether-based electrolyte.

25 ENERGY STORAGE↗
NASA NTRS1985

Polyfunctional epoxies. I - Rubber-toughened brominated and nonbrominated formulations for graphite composites. II - Nonrubber versus rubber-toughened brominated formulations for graphite composites

A new trifunctional epoxy resin, Tris-(hydroxyphenyl) methane triglycidyl ether, is compared to a state-of-the-art tetraglycidyl 4,4'-diaminodiphenyl methane (TGDDM), in graphite composites. Rubber-toughened brominated formulations of the epoxy resin are compared to nonbrominated ones in terms of their mechanical performance, environmental stability, thermochemical behavior, and flame retardancy. It is shown that the new resin performs almost the same way as the TGDDM does, but has improved glass transition temperature and environmental properties. Brominated polymeric additives (BPA) of different molecular weights are tested as a Br source to flame retardant graphite epoxy composites. The optimal molecular weight of the BPA and its polymeric backbone length are derived and compared with a 10 percent rubber-toughened formulation of the epoxy resin. Results indicate that when the Br content in the graphite composite is increased without the use of rubber, the mechanical properties improved. The use of BPAs as tougheners for graphite composites is also considered.

Nir, Z.↗
DOE OSTI2024

Tetraether archaeal lipids promote long‐term survival in extreme conditions

Abstract The sole unifying feature of the incredibly diverse Archaea is their isoprenoid‐based ether‐linked lipid membranes. Unique lipid membrane composition, including an abundance of membrane‐spanning tetraether lipids, impart resistance to extreme conditions. Many questions remain, however, regarding the synthesis and modification of tetraether lipids and how dynamic changes to archaeal lipid membrane composition support hyperthermophily. Tetraether membranes, termed glycerol dibiphytanyl glycerol tetraethers (GDGTs), are generated by tetraether synthase (Tes) by joining the tails of two bilayer lipids known as archaeol. GDGTs are often further specialized through the addition of cyclopentane rings by GDGT ring synthase (Grs). A positive correlation between relative GDGT abundance and entry into stationary phase growth has been observed, but the physiological impact of inhibiting GDGT synthesis has not previously been reported. Here, we demonstrate that the model hyperthermophile Thermococcus kodakarensis remains viable when Tes (TK2145) or Grs (TK0167) are deleted, permitting phenotypic and lipid analyses at different temperatures. The absence of cyclopentane rings in GDGTs does not impact growth in T. kodakarensis , but an overabundance of rings due to ectopic Grs expression is highly fitness negative at supra‐optimal temperatures. In contrast, deletion of Tes resulted in the loss of all GDGTs, cyclization of archaeol, and loss of viability upon transition to the stationary phase in this model archaea. These results demonstrate the critical roles of highly specialized, dynamic, isoprenoid‐based lipid membranes for archaeal survival at high temperatures.

Biochemistry & Molecular Biology↗
NASA NTRS2012

High-Temperature Shape Memory Polymers

physical conformation changes when exposed to an external stimulus, such as a change in temperature. Such materials have a permanent shape, but can be reshaped above a critical temperature and fixed into a temporary shape when cooled under stress to below the critical temperature. When reheated above the critical temperature (Tc, also sometimes called the triggering or switching temperature), the materials revert to the permanent shape. The current innovation involves a chemically treated (sulfonated, carboxylated, phosphonated, or other polar function group), high-temperature, semicrystalline thermoplastic poly(ether ether ketone) (Tg .140 C, Tm = 340 C) mix containing organometallic complexes (Zn++, Li+, or other metal, ammonium, or phosphonium salts), or high-temperature ionic liquids (e.g. hexafluorosilicate salt with 1-propyl-3- methyl imidazolium, Tm = 210 C) to form a network where dipolar or ionic interactions between the polymer and the low-molecular-weight or inorganic compound forms a complex that provides a physical crosslink. Hereafter, these compounds will be referred to as "additives". The polymer is semicrystalline, and the high-melt-point crystals provide a temporary crosslink that acts as a permanent crosslink just so long as the melting temperature is not exceeded. In this example case, the melting point is .340 C, and the shape memory critical temperature is between 150 and 250 C. PEEK is an engineering thermoplastic with a high Young fs modulus, nominally 3.6 GPa. An important aspect of the invention is the control of the PEEK functionalization (in this example, the sulfonation degree), and the thermal properties (i.e. melting point) of the additive, which determines the switching temperature. Because the compound is thermoplastic, it can be formed into the "permanent" shape by conventional plastics processing operations. In addition, the compound may be covalently cross - linked after forming the permanent shape by S-PEEK by applying ionizing radiation ( radiation, neutrons), or by chemical crosslinking to form a covalent permanent network. With respect to other shape memory polymers, this invention is novel in that it describes the use of a thermoplastic composition that can be thermally molded or solution-cast into complex "permanent" shapes, and then reheated or redissolved and recast from solution to prepare another shape. It is also unique in that the shape memory behavior is provided by a non-polymer additive.

Yoonessi, Mitra↗
NASA NTRS1983

Determination of physical and chemical states of lubricants in concentrated contacts, part 3

Solid and liquid thin films were analyzed by infrared emission Fourier microspectrophotometry. The apparatus used is a commercial absorption instrument modified to an emission instrument, comprising a rotating polarizing device, a miniature blackbody temperature reference adjustable in temperature and radiant flux and a microscope lens with a high numerical aperture in the entrance system for increased sensitivity and resolution. Studies of lubricant behavior in a simulated ball bearing showed the alignment of the fluid molecules in the Hertzian area. Polyphenyl ether plus 1% 1,1,2-trichloroethane (TCE) required lower shear rates for the same degree of alignment than without TCE. The experiment was run with 440 C stainless steel balls coated with TiN, a chemically inert material. In both cases, the alignment was strongly influenced by the presence of TCE. The results showed (1) the dependence of alignment of fluid molecules on flow and not on adsorption at metallic surfaces, (2) phase separation between lubricant and additive under high pressure which results in two phase flow and (3) reduction in traction of torque transmitting (traction) fluids.

Lauer, J. L.↗
DOE OSTI2023

Diesel fuel properties of renewable polyoxymethylene ethers with structural diversity

Polyoxymethylene ethers (POMEs) are a class of low-soot and high-cetane oxygenate oligomers of structure RO-(CH 2 O-) $n$ -R, with different chain lengths ($n$) and end-groups (R) that determine their diesel-like fuel properties. Commercial POMEs with methyl end-groups (MM-POME 3-6 ) exhibit undesirably low energy density and high-water solubility. A previous computational assessment indicated that the lower heating value (LHV) and water solubility for MM-POME 3-6 both improve upon end-group exchange with larger butyl, $iso$-butyl and $iso$-pentyl end-groups. Here, we expanded upon our initial trans-acetalization reaction that employed 1-butanol to install butyl end-groups to also include branched, higher carbon-number end-groups using $iso$-butanol and fusel oil as reagents. Additionally, these new products are termed $i$B*POME 1-6 , and FOil*POME 1-5 , respectively, and collectively referred to as R*POMEs. They possess the advantaged properties of the parent MM-POME 3-6 while exhibiting higher LHV (31 MJ kg -1 and 28 MJ kg -1 for $i$B*POME 1-6 , and FOil*POME 1-5 , respectively) and much reduced water solubility (2.7 g L -1 and 1 g L -1 for $i$B*POME 1-6 , and FOil*POME 1-5 , respectively). Additional fuel property analyses were performed using 20 vol% blends of the R*POMEs with a base diesel fuel. Overall, the greater energy density and decreased water solubility of the R*POMEs, as well as their synergistic blending with diesel at moderate blend levels, provide the greatest benefits to consumers and position this group of products as an environmentally friendlier blendstock alternative to the commercially available MM-POME 3-6 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Influence of Charge Fraction on the Phase Behavior of Symmetric Single-Ion Conducting Diblock Copolymers

A series of symmetric poly[(oligo(ethylene glycol) methyl ether methacrylate-co-oligo(ethylene glycol) propyl sodium sulfonate methacrylate)]-block-polystyrene (PsOEGMA-PS) diblock copolymers were synthesized as a model system to probe the effect of charge fraction on the phase behavior of charged-neutral single-ion conducting diblock copolymers. Small-angle X-ray scattering (SAXS) experiments showed that increasing the charge fraction does not alter the ordered phase morphology (lamellar) but increases the order–disorder transition temperature (T ODT ) significantly. Additionally, the effective Flory–Huggins interaction parameter (χ eff ) was found to increase linearly with the charge fraction, similar to the case of conventional salt-doped diblock copolymers. This indicates that the effect of counterion solvation, attributed to the significant mismatch between the dielectric constant of each block, provides the dominant effect in tuning the phase behavior of this charged diblock copolymer. Lastly, we therefore infer that electrostatic cohesion (local charge ordering induced by Coulombic interactions), which is predicted to suppress microphase separation and lead to asymmetric phase diagrams, only plays a minor role in this model system.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Catalytic Activity of Ti-based MXenes for the Hydrogenation of Furfural

Here, we report on the catalytic activity of Ti-based MXenes (Ti 3 CNT z and Ti 3 C 2 T z ) for biomass transformation. MXenes were found to be active catalysts for the hydrogenation of furfural using either gaseous hydrogen or 2-propanol as solvent and hydrogen source. Both catalysts showed good activity in the conversion of furfural to furfuryl alcohol, with furfuryl ether as the main by-product. Stability tests indicated that Ti 3 CNT z is more stable than Ti 3 C 2 T z against deactivation. Ab initio calculations were used to examine the hydrogenation and etherification reactions pathways and their corresponding reaction energetics on the Ti 3 CNT z MXene. The results indicate that the hydrogenation of the carbonyl bond efficiently proceeds via the heterolytic activation of hydrogen over the metal-oxygen site pair followed by the addition of the proton and hydride to the C and O atoms of the carbonyl. The subsequent hydrogenation of the unsaturated furan ring via metal bound hydrogen, however, is calculated to be much more difficult. Protons bound to the oxygen of the MXene are acidic and can also catalyze the etherification of the resulting alcohols. Finally, the bifunctional acid-metal site pairs also selectively catalyze the hydrogenolysis of the furfuryl alcohol to form 2-methyl furan.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1989

Polyimides containing carbonyl and ether connecting groups - II

In a study of polyimides containing carbonyl and ether connecting groups between aromatic rings, several new polyimides were prepared and characterized. A few of these polymers were semicrystalline. Glass transition temperatures ranged from 164 to 258 C, and crystalline melt temperatures were observed between 350 and 424 C. The semicrystalline polyimide from the reaction of 3.3',4,4'-benzophenonetetracarboxylic dianhydride and 1,3-bis(4-aminophenoxy-4'-benzoyl)benzene provided transparent orange films with excellent tensile properties, exceptional resistance to solvents and strong base, and high thermooxidative stability. In addition, this polyimide provided excellent adhesive strength for joining titanium (6Al-4V) to titanium.

Hergenrother, P. M.↗
NASA NTRS1997

HFE 7100 Compatibility with Orbiter Materials

Chlorofluorocarbon (CFC) 113 is currently specified as the precision cleaning and verification fluid for orbiter materials. The production ban of CFC 113, an ozone-depleting chlorofluorocarbon, has resulted in a search for a replacement cleaning fluid. Recently, the 3M Company announced the manufacture of a new class of cleaning fluids, hydrofluoroethers. The first in this class of cleaning fluids is HFE 7100, perfluorobutyl methyl ether. This cleaning fluid has been submitted for consideration as a replacement for CFC 113. One of the requirements of the certification process for a replacement cleaning fluid is compatibility testing. The Johnson Space Center (JSC) Materials and Manufacturing Division has requested that NASA JSC White Sands Test Facility perform the compatibility testing with HFE 7100 on selected orbiter materials. Most of the materials selected for testing were previously evaluated for compatibility with CFC 113. Some of the materials are new additions to the orbiter or were not available when the compatibility testing was performed with CFC 113. These materials were evaluated with both cleaning fluids and the results were used to compare the response to the cleaning fluid and to satisfy the certification process requirements. It was found that HFE 7100 is generally compatible with the materials tested.

Chlorofluorocarbon↗
NASA NTRS1999

Effects of Melt Processing on Evolution of Structure in PEEK

We report on the effects of melt processing temperature on structure formation in Poly(ether-ether-ketone), PEEK. Real time Small Angle X-ray Scattering, SAXS, and thermal analysis are used to follow the melting behavior after various stages of processing. Assignment of peaks to structural entities within the material, the relative perfection of the crystals, and the possibility of their reorganization, are all influenced by the melt processing history. With the advent of high intensity synchrotron sources of X-radiation, polymer scientists gain a research tool which, when used along with thermal analysis, provides additional structural information about the crystals during growth and subsequent melting. PEEK is an engineering thermoplastic polymer with a very high glass transition temperature (145 C) and crystal melting point (337 C). PEEK has been the subject of recent studies by X-ray scattering in which melt and cold crystallization were followed in real-time. X-ray scattering and thermal studies have been used to address the formation of dual endothermic response which has been variously ascribed to lamellar insertion, dual crystal populations, or melting followed by re-crystallization. Another important issue is whether all of the amorphous phase is located in interlamellar regions, or alternatively whether some is located in "pockets" away from the crystalline lamellar stacks. The interpretation of scattering from lamellar stacks varies depending upon whether such amorphous pockets are formed. Some groups believe all of the amorphous phase is interlamellar. This leads to selection of a smaller thickness for the crystals. Other groups suggest that most amorphous phase is not interlamellar, and this leads to the suggestion that the crystal thickness is larger than the amorphous layer within the stacks. To investigate these ideas, we used SAXS and Differential Scanning Calorimetry to compare results of single and dual stage melt crystallization of PEEK using a treatment scheme involving annealing/crystallization at T(sub a1) followed by annealing at T(sub a2) where either T(sub a1) < T(sub a2) or T(sub a1) > T(sub a2). We proposed a model to explain multiple melting endotherms in PPS, treated according to one or two-stage melt or cold crystallization. Key features of this model are that multiple endotherms: (1) are due to reorganization/recrystallization after cold crystallization; and, (2) are dominated by crystal morphology after melt crystallization at high T. In other words, multiple distinct crystal populations are formed by the latter treatment, leading to observation of multiple melting. PEEK 45OG pellets (ICI Americas) were the starting material for this study. Films were compression molded at 400 C, then quenched to ice water. Samples were heated to 375 C in a Mettler FP80 hot stage and held for three min. to erase crystal seeds before cooling them to T(sub a1) = 280 C . Samples were held at T(sub a2) for a period of time, then immediately heated to 360 C. In the second treatment samples were held at T(sub a1) = 31 C for different crystallization times t(sub c) then cooled to 295 C and held 15 min. In situ (SAXS) experiments were performed at the Brookhaven National Synchrotron Light Source with the sample located inside the Mettler hot stage. The system was equipped with a two-dimensional position sensitive detector. The sample to detector distance was 172.7 cm and the X-ray wavelength was 1.54 Angstroms. SAXS data were taken continuously during the isothermal periods and during the heating to 360 C at 5 C/min. Each SAXS scan was collected for 30 sec. Since the samples were isotropic, circular integration was used to increase the signal to noise ratio. After dual stage melt crystallization with T(sub a1) < T(sub a2) the lower melting endotherm arises from holding at T(sub a1). During cooling a broad distribution of crystals forms, and the low-melting tail is perfected during T(sub al). Heating to T(sub a2) melts these imperfect crystals and allows others with greater average long spacing to form in their place. After dual stage crystallization with T(sub a1) > T(sub a2), the amount of space remaining for additional growth at T(sub a2) depends upon the holding time at T(sub a1). The long period of crystals formed at T(sub a2) is smaller than that formed at T(sub a1) due to growth in a now-restricted geometry. Perfection of crystals is seen as an increase of the intensity of the population scattering at higher s, while the intensity of the population scattering at lower s stays constant. During heating from below to above the minor endotherm, we see rapid decrease of the intensity of the X-ray scattering corresponding to the population of crystals scattering in the shoulder. Another important observation is that after the sample is annealed at 295 C, the shoulder intensity is restored once again. The population scattering at higher s remains longer before it disappears in the sample treated to the second stage of melt crystallization, compared to the sample crystallized with a single stage. This could be interpreted as an effect of continued perfection of the less perfect population, which is also reflected in the increased melting temperature of the smaller endotherm as the holding time at 295 C increases. In the corresponding DSC scans we see a shift in the area and the peak temperature of the lower melting endotherm with an increase of the annealing time.

Georgiev, Georgi↗
DOE OSTI2023

Enhancing durability of polymer electrolyte membrane using cation size selective agents

Radical species generated during proton exchange membrane fuel cell operation considerably limit the achievable durability, particularly for heavy-duty vehicle applications. A promising solution to the problem is the incorporation of radical scavenger additives such as cerium which mitigates chemical attacks on the membrane. However, these additives migrate during fuel cell operation causing a loss in durability and performance due to detrimental interaction with various components of the fuel cell. Here, we study cation size selective agents as a means to immobilize cerium within perfluorosulfonic acid (PFSA) membranes. We synthesized an organometallic complex of cerium with 15-Crown-5 and investigated the effectiveness of this complex to immobilize cerium. Over 300% increase in cerium retention and an 80% increase in chemical durability were observed owing to the stabilization effect of crown ethers on cerium. Migration under a potential gradient can be eliminated while the complex also contributes to the enhancement in cerium radical scavenging activity. In conclusion, current challenges with the proposed solution are highlighted and future work is discussed.

25 ENERGY STORAGE↗
DOE OSTI2026

Flame dynamics and kinetic coupling of ammonia and dimethyl-ether in non-premixed cool and warm flames at elevated pressure

Developing advanced low-temperature combustion engines with ammonia-biofuel blends requires a comprehensive understanding of low-temperature flame dynamics and kinetic interactions between ammonia and oxygenated fuels at elevated pressures. This work aims to study the dynamics and kinetics of non-premixed Dimethyl Ether (DME)/Ammonia (NH 3 ) cool and warm flames, and their reignition to hot flames. A counterflow burner is employed to establish DME/NH 3 cool/warm flames at pressures up to 5 atm. The extinction limits of cool flame and the reignition limits of warm flame to hot flame are measured by varying NH 3 concentrations and compared to simulations to quantitatively examine the effects on DME/NH 3 flames. It is found that NH 3 inhibits low-temperature DME oxidation and results in lower cool flame extinction limits. Warm flames in the presence of NH 3 are observed for the first time, revealing a non-monotonic effect of NH 3 addition: a small amount of NH 3 presence enhances warm flame chemistry and promotes reignition to hot flames, while a high NH 3 concentration weakens the warm flame. This trend is further explained by 0-D PSR kinetic simulations and 1-D S-curve flame dynamic calculations. Three flame transition regimes between cool flames (CF), warm flames (WF), and hot flames (HF) by different levels of NH 3 additions at a specific strain rate are identified, namely WFHF reignition, WF-CF transition, and WF extinction. Reaction sensitivity analyses of OH at low temperatures show that NH3 inhibits DME oxidation through OH consumption via H-abstraction and the kinetic couplings of RO 2 /NH 2 , RO 2 /NO x , R/NO x , and O 2 QOOH/NO x further suppress the low-temperature branching. At intermediate-temperatures, NH 2 /NO x /HO 2 coupling promotes warm flames via the pathway NH 2 → H 2 NO → HNO → NO by converting O 2 → HO 2 → OH. At even higher NH₃ concentrations, radical termination reactions of NH 2 + NO/NO 2 and excessive OH consumption via H-abstraction inhibit the flame. The insights into the kinetic coupling between NH 3 and low-temperature chemistry at elevated pressure and its impact on the dynamics of cool-warm-hot flame transitions will contribute to advancing combustion technologies with reduced emissions and improved energy-efficiency.

42 ENGINEERING↗
DOE OSTI2022

Porous Liquids as Electrolyte: A Case Study of Li + and Mg 2+ Ion Transport in Crown Ether-Based Type-II Porous Liquids

Here, we demonstrate crown ether (CE)-based type II porous liquid (PL) electrolytes in which CEs provide internal porosity and are capable of coordinating with Li + and Mg 2+ ions. We investigated the physicochemical properties of the PL electro-lytes with different functional groups and cavity sizes. Among the electrolytes studied, the 12-crown-4 (12C4)-based PL electrolyte exhibited the most enhanced ionic conductivity due to size match between the CE cavity and the Li + ion. Nu-clear magnetic resonance and Fourier transform infrared analyses revealed that addition of CEs reduces the Li + ion–solvent interaction, resulting in the formation of Li-CE complexes. The simulation study clearly showed that the solvated Li + and Mg 2+ ions form complexes with 12C4. The strategy described here using CE-based PLs should be applicable to the design versatile electrolytes for various metal-ion batteries.

Shin, Sun Hae Ra↗