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At least 37 records · Page 2

Environmental sensitivities of shallow-cumulus dilution – Part 2: Vertical wind profile

This second part of a numerical study on shallow-cumulus dilution focuses on the sensitivity of cloud dilution to changes in the vertical wind profile. Insights are obtained through large-eddy simulations of maritime and continental cloud fields. In these simulations, the speed of the initially uniform geostrophic wind and the strength of geostrophic vertical wind shear in the cloud and subcloud layer are varied. Increases in the cloud-layer vertical wind shear (up to 9 ms -1 km -1 ) lead to 40%–50% larger cloud-core dilution rates compared to their respective unsheared counterparts. When the background wind speed, on the other hand, is enhanced by up to 10 ms -1 and subcloud-layer vertical wind shear develops or is initially prescribed, the dilution rate decreases by up to 25%. The sensitivities of the dilution rate are linked to the updraft strength and the properties of the entrained air. Increases in the wind speed or vertical wind shear result in lower vertical velocities across all sets of experiments with stronger reductions in the cloud-layer wind shear simulation (27%–47%). Weaker updrafts are exposed to mixing with the drier surrounding air for a longer time period, allowing more entrainment to occur (i.e., the “core-exposure effect”). However, reduced vertical velocities, in concert with increased cloud-layer turbulence, also assist in widening the humid shell surrounding the cloud cores, leading to entrainment of more humid air (i.e., the “core–shell dilution effect”). In the experiments with cloud-layer vertical wind shear, the core-exposure effect dominates and the cloud-core dilution increases with increasing shear. Conversely, when the wind speed is increased and subcloud-layer vertical wind shear develops or is imposed, the core–shell dilution effect dominates to induce a buffering effect. The sensitivities are generally stronger in the maritime simulations, where weaker sensible heat fluxes lead to narrower, more tilted, and, therefore, more suppressed cumuli when cloud-layer shear is imposed. Moreover, in the experiments with subcloud wind shear, the weaker baseline turbulence in the maritime case allows for a larger turbulence enhancement, resulting in a widening of the transition zones between the cores and their environment, leading to the entrainment of more humid air.

54 ENVIRONMENTAL SCIENCES↗

Temperature-Dependent Communication between Pt/Al 2 O 3 Catalysts and Anatase TiO 2 Dilutant: the Effects of Metal Migration and Carbon Transfer on the Reverse Water–Gas Shift Reaction

In heterogeneous catalysis, unexpected effects from the supposedly inert reactor dilutant are not rare, but related understanding is lacking and inconsistent. Here we report investigations of the impacts of the anatase TiO 2 dilutant on the reverse water-gas shift (rWGS) reaction over Pt/Al 2 O 3 catalysts. Combining detailed kinetic data with microscopic and spectroscopic results, we demonstrate that the catalyst-dilutant communication depends on temperature. At high temperature (400 °C), Pt migrate from Al 2 O 3 to TiO 2 , resulting in higher dispersion and activity, without changing reaction mechanisms. The Pt migration is general to catalysts of different Pt nuclearity and various oxide dilutants. In contrast, at low temperature (250 °C), carboxylic acids (in particular acetic acid) present in the ambient air and adsorbed on TiO 2 are transferred onto Al 2 O 3 in close contact, effectively blocking the formate rWGS pathway. As a result, the rWGS can only proceed through the carboxyl pathway, and hence is significantly slower. The acetate transfer affects catalysts of different Pt nuclearity and support, but is unique to anatase TiO 2 dilutant. As the acetate layer is slowly removed under H 2 or the rWGS stream, the activity recovers. This work elucidates the complicated communication between catalysts and dilutants, which has general implications in heterogeneous catalysis, and resolves inconsistency in related reports in the literature. Finally, the impacts that anatase TiO 2 dilution has on the rWGS also unveil mechanistic understanding that further confirms the two co-existing rWGS pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of dilution and pressure on combustion characteristics within externally heated micro-tubes

Here this study investigates the impact of pressure and dilution on combustion behavior of of C 2H6/air/N2 mixtures within an externally heated micro-tube using both experimental and analytical techniques. Experiments are conducted for pressures up to 10 bar at multiple dilution levels and document three flame regimes, i.e. weak flames, FREI and normal flames. Characteristic temperatures for flame stabilization, as well as and ignition and extinction are obtained by applying a novel thin filament pyrometry method (TFP), which uses a thin silicon carbide (SiC) filament that enables temperature measurements for both reacting and non-reacting cases. Results show a decrease of characteristic temperatures with increasing pressure, which can be which can be partially compensated by a decrease of O2 content. Further, regime transitions occur at lower velocity as the pressure increases, whereas weak flame positions are insensitive to dilution at a given pressure. Predictions from the analytical model compare favorably with experimental results. The most prominent finding is that as dilution increases, the transition from weak flame to FREI becomes less abrupt and is completely lost for high dilution levels (i.e. low O2 content). Both experimental and analytical results indicate that the unstable FREI combustion regime does not exist at high dilution levels, i.e. weak flame and normal flame regimes are no longer clearly separated. As FREI are interpreted as a cyclic transition from an ignition zone to a propagating flame, results for highly diluted conditions are interpreted as a combustion regime where classical flame propagation ceases to exist.

42 ENGINEERING↗

Exploring the Effects of Varying Pre-Chamber Geometry in a Heavy-Duty Natural Gas Optical Engine under Dilution Conditions

Pre-chamber combustion is an advanced ignition strategy that has been shown to enhance spark ignition (SI) combustion stability in natural gas (NG) engines by providing distributed ignition sites from turbulent jets and enhancing main-chamber turbulence. Pre-chamber combustion has been proven especially advantageous compared to SI in ultra-lean and dilute operating conditions. This work involves experimental investigation of the effects of varying passive pre-chamber nozzle configuration on pre-chamber and main chamber combustion under simulated exhaust gas recirculation (EGR) dilution (0 and 20%) conditions in a heavy-duty, single-cylinder, optically accessible NG engine at stoichiometric fuel-air ratio. Pre-chamber nozzle configurations include four pre-chambers with constant nozzle area to pre-chamber volume ratio (A/V) with different nozzle sizes and orientations and one configuration with larger nozzles. The optical engine is operated in a skip-fire sequence consisting of 18 motored cycles followed by two consecutive fired cycles to elucidate the effect of combustion residuals (internal EGR) on combustion evolution. Pressure-based diagnostics are used to monitor pre-chamber and subsequent main chamber combustion, and optical diagnostics include high-speed OH* chemiluminescence to visualize the development of pre-chamber jets and the resulting ignition of the main chamber charge. Heat release analysis of the in-cylinder pressure data indicates that a faster pre-chamber pressure rise does not always translate into faster main-chamber combustion. The pre-chamber with the smallest nozzle diameter produced the highest pre-chamber pressure rise and fastest combustion under non-diluted conditions. However, dilution delays the main chamber ignition for smaller nozzles despite a comparable rise in pre-chamber pressure compared to configurations with larger nozzles. This effect is more pronounced for cycles with in-cylinder combustion residuals in addition to external dilution. Additionally, it was observed that pre-chambers with swirling nozzles have a faster pressure rise in the pre-chamber and main chamber under dilute conditions. Optical diagnostics suggest that the main reason for the delay between the pre-chamber pressure rise and main-chamber combustion lies in jet quenching and delayed re-ignition, which can even lead to misfire if jets emitted from small nozzles combined with dilution fail to re-ignite.

Dhotre, Akash [University Of Minnesota-Twin Cities↗

Impact of dilution on microbial community structure and functional potential: comparison of numerical simulations and batch culture experiments

A series of microcosm experiments was performed using serial dilutions of a sewage microbial community to inoculate a set of batch cultures in sterile sewage. After inoculation, the dilution-defined communities were allowed to regrow for several days and a number of community attributes were measured in the regrown assemblages. Based upon a set of numerical simulations, community structure was expected to differ along the dilution gradient; the greatest differences in structure were anticipated between the undiluted-low-dilution communities and the communities regrown from the very dilute (more than 10(-4)) inocula. Furthermore, some differences were expected among the lower-dilution treatments (e.g., between undiluted and 10(-1)) depending upon the evenness of the original community. In general, each of the procedures used to examine the experimental community structures separated the communities into at least two, often three, distinct groups. The groupings were consistent with the simulated dilution of a mixture of organisms with a very uneven distribution. Significant differences in community structure were detected with genetic (amplified fragment length polymorphism and terminal restriction fragment length polymorphism), physiological (community level physiological profiling), and culture-based (colony morphology on R2A agar) measurements. Along with differences in community structure, differences in community size (acridine orange direct counting), composition (ratio of sewage medium counts to R2A counts, monitoring of each colony morphology across the treatments), and metabolic redundancy (i.e., generalist versus specialist) were also observed, suggesting that the differences in structure and diversity of communities maintained in the same environment can be manifested as differences in community organization and function.

Non-NASA Center↗

Optimized Illuminance Operation-A Light-Driven Dilution Strategy to Improve Microalgae Biomass Productivity

Periodic dilution is a necessary operation to avoid light limitation due to self-shading as the culture grows dense. However, environmental conditions are constantly changing in outdoor cultivation systems, making it difficult to determine the optimal dilution rate. To address this challenge, this study evaluated a dilution approach based on light penetration to optimize illuminance (OptiLum) in the culture. Biomass concentration was controlled via sensor-feedback directed dilution to ensure that light reaching the bottom of the culture was maintained above the compensation intensity. Under replicated outdoor pond conditions, by keeping the entire culture within a net-positive photosynthetic zone, the OptiLum operation improved the biomass productivities of two top-performing strains, Picochlorum celeri and Tetraselmis striata, by 95 % and 86 %, respectively, compared to conventional semi-continuous batch cultivation. The dilution rate varied daily and was dynamically adjusted based on the light status within the culture, which is concurrently influenced by weather, culture density, and growth rate. The techno-economic analysis showed that the OptiLum operation could reduce biomass production cost by as much as 24 % and 33 % for P. celeri and T. striata, respectively, assuming a low-cost dewatering approach with initial gravity settling of biomass can be realized for both strains. However, a more costly two-stage dewatering strategy, comprising only membranes and centrifuges, may be necessary for non-settling strains, such as P. celeri, which would alternatively increase production costs by 23 % for the OptiLum case. The results demonstrated that the proposed OptiLum operation is a promising approach to improve biomass productivity and lower production cost via weather-responsive and self-adjusting dilution.

09 BIOMASS FUELS↗

Impact of dilution-induced precipitates on the filtration of Hanford liquid tank wastes

To facilitate its vitrification, a portion of the radioactive wastes currently stored at the Hanford Site will be staged and treated using tank-side operations to render their chemistry compliant with the requirements of Hanford’s low-activity waste vitrification facility. Initial sampling of staged feeds indicates that process-water dilution, used to reduce waste feed sodium content to levels acceptable for vitrification (5–6 M Na), may cause precipitation of fine, difficult to settle solids that could affect downstream tank-side filtration and ion-exchange. However, dilution-induced precipitation has not been demonstrated under controlled, rigorous laboratory conditions. This paper presents a set of qualitative and quantitative assessments of dilution-induced precipitation using a nonradioactive, Hanford Tank AP-105 simulated waste. Further, these studies found that dilution of AP-farm waste simulants induced precipitation of up to 150 ppm solids, regardless of whether dilution was done with process water (which contains, among other analytes, naturally occurring Ca and Mg) or deionized water. Naturally occurring process-water analytes appeared to accelerate the rate (and possibly extent) of precipitation. Filtration of diluted waste simulants also found that the precipitated solids challenged prototypic tank-side filter operations; however, the impact to filtration performance was readily managed through waste staging settle/decant operations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Light Dark Matter from Entropy Dilution

We show that a thermal relic which decouples from the standard model (SM) plasma while relativistic can be a viable dark matter (DM) candidate, if the decoupling is followed by a period of entropy dilution that heats up the SM, but not the dark sector. Such diluted hot relics can be as light as few keV, while accounting for the entirety of the DM, and not conflicting with cosmological and astrophysical measurements. The requisite dilution can be achieved via decays of a heavy state that dominates the energy budget of the universe in the early matter dominated era. The heavy state decays into the SM particles, heats up the SM plasma, and dilutes the hidden sector. The interaction required to equilibrate the two sectors in the early universe places a bound on the maximum possible dilution as a function of the decoupling temperature. As an example of diluted hot relic DM we consider a light Dirac fermion with a heavy dark photon mediator. We present constraints on the model from terrestrial experiments (current and future), astrophysics, and cosmology.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Unraveling 1-Hexene Hydrogenation over Dilute Pd-in-Au Alloys

Dilute Pd-in-Au alloys are valuable materials for selectively hydrogenating alkynes and isomerizing alkenes. By diluting Pd in a Au host, the selectivity toward semihydrogenated alkene isomers can be significantly enhanced and the unfavorable overhydrogenation to alkanes is suppressed. However, a detailed mechanistic study on the origin of the enhanced alkene selectivity over dilute alloy catalysts is still missing. Here, we combine experiment and theory to unravel the reaction mechanism, identifying rate-limiting and selectivity-controlling steps in 1-hexene hydrogenation over dilute Pd-in-Au catalysts. Using isotope-exchange hydrogenation experiments, we show that 1-hexene and hydrogen over a bimetallic Pd4Au96 in silica catalyst preferentially form 1-hexene isomers, (trans and cis) 2- and 3-hexene and only a small amounts of hexane. The reaction is consistent with a Horiuti–Polanyi mechanism, similar to a monometallic Pd nanoparticle catalyst. Computation of the free-energy profiles for 1-hexene hydrogenation and isomerization over a single Pd atom in a Au surface using first principles calculations indicated that the isomerization of 1-hexene to 2-hexene is energetically favorable due to the relatively large barrier for H2 dissociation preventing hydrogenation to n-hexane. Microkinetic modeling established that H2 dissociation on the single-atom Pd sites and H spillover from these sites onto the Au host are rate-limiting and key in steering the selectivity of dilute Pd-in-Au alloys toward the hexene isomers. Furthermore, the mechanistic insights from this study contribute to the rational design of optimized dilute alloy catalysts for selective alkene isomerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deliquescence of Eutectic LiCl-KCl Diluted with NaCl for Interim Waste Salt Storage

Molten eutectic LiCl-KCl salt is a widely used electrolyte for electrorefining uranium from spent nuclear fuel. Due to the hygroscopic nature of this salt, such operations must be performed under controlled atmospheric conditions, and waste salts require careful storage to avoid deliquescence and corrosion of container materials. This study investigated a potential processing path for reducing the degree of deliquescence through dilution to varying extents with NaCl. Here, the hydration behavior of LiCl-KCl salts diluted with NaCl was evaluated in terms of mass gain due to water absorption, degree of deliquescence (including first appearances of standing water), and evidence of corrosion to stainless steel containers in a humid air environment (40°C, 20% relative humidity). In this humid air environment, pure eutectic LiCl-KCl exhibited a 50 mass % increase due to water absorption and showed evidence of standing water after 24 h. Waste salt diluted with NaCl required loadings of 89 mass % NaCl in order to prevent deliquescence and exhibited a 3 mass % increase due to water absorption. After periodic observation for 48 h, standing water was observed near all ingots with the exception of the 89 mass % NaCl samples. Dilution with 89% NaCl was also found to reduce evidence of corrosion when stored in stainless steel crucibles. While dilution with NaCl greatly decreases steady-state hydration, the storage volume is increased ~10× through this procedure.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Investigations into EGR dilution tolerance in a pre-chamber ignited GDI engine

EGR is a useful means to improve fuel economy in spark-ignited gasoline engines, especially under part-load conditions by means of reducing throttling losses. There is also a significant reduction in NOx emissions due to the reduced peak cylinder temperatures. However, the ability of conventional spark ignition systems to reliably ignite dilute mixtures limits the dilution tolerance due to the onset of combustion instability. In this study, an active pre-chamber system was evaluated at part load condition with various EGR rates using a regular grade full boiling range gasoline. A premixed air-fuel mixture was supplied to the pre-chamber, which assists in scavenging the residual mass fractions to enable reliable ignition of EGR dilute mixtures in the main combustion chamber. A range of pre-chamber injection, air-fuel mixture formulation, and ignition timing strategies were evaluated during the EGR sweeps. In addition, 0-D and 1-D simulations were conducted in GT-Power to assess the thermodynamic state and composition in the pre-chamber, as well as estimate the jet momentum at the various dilution rates. The active pre-chamber extended the EGR dilution limit from 20% for conventional SI to above 30%, with a higher pre-chamber flow rate (more scavenging) resulting in increased combustion stability. A tradeoff between the jet momentum and spark timing was observed when analyzing the GT-Power simulations and the pre-chamber jet momentum was found to decrease with increasing EGR rate. At unstable high EGR operation, no relation could be found between the pre-chamber indicated data and main chamber combustion stability.

33 ADVANCED PROPULSION SYSTEMS↗

Dilute and Dispose Cost Estimate for Equipment Installation per the LCCE

As directed in the Consolidation Appropriations Act, 2016, the National Nuclear Security Administration (NNSA) initiated the preconceptual design and development of a Lifecycle Cost Estimate for the Surplus Plutonium Disposition (SPD) Dilute and Dispose Program. Based on August 2016 Program Requirements Document and subsequent supplemental guidance, LANL prepared the Lifecycle Cost Estimate under key assumptions that meet the program’s requirements. For Dilute and Dispose, the program would disposition surplus Pu by diluting oxide produced at LANL with inhibitor materials, packaging the materials in containers, and shipping the containers to a deep geologic repository for permanent disposal. The base assumption is that LANL would disassemble pits, convert the Pu metal to oxide, and characterize and package the material for shipment to SRS, where it would be diluted prior to geologic disposal at the WIPP site in New Mexico. Another major assumption for the Dilute and Dispose option is that LANL would increase the current oxide production rate (or throughput) to 1500 kg/year, 5 times higher than the maximum annual production of ~300 Kgs executed by the ARIES Oxide Production Program at LANL. Analysis based on the ARIES program’s throughput model revealed that 15 pieces of equipment would need to be installed within PF-4 and certain facility improvements would need to be accomplished in order to meet the desired throughput levels. The additional equipment would be essentially identical to equipment already used within PF-4 for existing operations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

EGR Dilution and Fuel Property Effects on High-Efficiency Spark-Ignition Flames

Modern spark ignition internal combustion engines rely on fast combustion rates and high dilution to achieve high brake thermal efficiencies. To accomplish this, new engine designs have moved towards increased tumble ratios and stroke-to-bore ratios. Increased tumble ratios correlate positively with increases in turbulent kinetic energy and improved fuel and residual gas mixing, all of which favor faster and more efficient combustion. Longer stroke-to-bore ratios allow higher geometric compression ratios and use of late intake valve closing to control peak compression pressures and temperatures. The addition of dilution to improve efficiency is limited by the resulting increase in combustion instabilities manifested by cycle-to-cycle variability. A number of effects - preferential diffusion, turbulence-combustion interactions, stochastic flow patterns, laminar-turbulent flame kernel transitions, and relative length and velocity scales between flame and turbulence - are believed to be responsible for the increase in cycle-to-cycle variations, where their contributions are likely interlinked. Several studies have shown the influence of stochastic flow characteristics on the nature of combustion instabilities, such as velocity patterns on flame kernel formation and cycle-to-cycle variations in residual gas. However, few have focused on the specific effects of fuel properties. The objective of this work is to contrast the effects of dilution on propane stoichiometric combustion against gasoline. Dilution tolerance experiments were conducted in a purpose-built high stroke-to-bore ratio single cylinder engine with both gasoline and LPG. Three-dimensional full cycle computational fluid dynamics (CFD) simulations employing a level-set combustion approach and Reynolds averaged Navier-Stokes (RANS) turbulence modeling was used to qualitatively assess the changes in length and velocity scales for turbulence and the flame. The experimental results showed that LPG can tolerate higher exhaust gas recirculation (EGR) dilution under a variety of conditions. Analysis of CFD simulations showed that propane flames are likely less sensitive to influences from the flow field due to less thickening of the flame and higher effective flame speeds.

33 ADVANCED PROPULSION SYSTEMS↗

In Situ Laser Induced Florescence Measurements of Fuel Dilution from Low Load to Stochastic Pre Ignition Prone Conditions

This work employs a novel laser induced fluorescence (LIF) diagnostic to measure fuel dilution in a running single cylinder research engine operated at stochastic pre ignition (SPI) and non-SPI prone conditions. Measurements of LIF based fuel dilution are quantified over a range of engine loads and fuel injection timings for two fuels. The in situ LIF measurements of fuel/lubricant interactions illustrate regions of increased fuel dilution from fuel-wall interactions and is believed to be a fundamental underpinning to generating top ring zone liquid conditions conducive to SPI. Furthermore, a novel level of dye doped in the fuel, between 50 to 500 ppm was used as the fluorescence source, at engine operating speed of 2000r/min from 5 to 18 bar of IMEPg injection timings was swept for two fuels of varying volatility. The direct real time LIF measurements highlight that there are non-linear trends in fuel dilution beyond simple dependencies of fuel volatility, injection duration or injection timing, suggesting that further understanding of spray interaction with engine surfaces and the turbulent field are needed to quantify fuel dilution effects that are conducive to SPI. Moreover, results show the potential of this diagnostic technique as an additional tool for quantifying spray and fuel mixing in fundamental studies deployable across a variety of engine loads from law to full load.

47 OTHER INSTRUMENTATION↗

Total body water and lean body mass estimated by ethanol dilution

A method for estimating total body water (TBW) using breath analyses of blood ethanol content is described. Regression analysis of ethanol concentration curves permits determination of a theoretical concentration that would have existed if complete equilibration had taken place immediately upon ingestion of the ethanol; the water fraction of normal blood may then be used to calculate TBW. The ethanol dilution method is applied to 35 subjects, and comparison with a tritium dilution method of determining TBW indicates that the correlation between the two procedures is highly significant. Lean body mass and fat fraction were determined by hydrostatic weighing, and these data also prove compatible with results obtained from the ethanol dilution method. In contrast to the radioactive tritium dilution method, the ethanol dilution method can be repeated daily with its applicability ranging from diseased individuals to individuals subjected to thermal stress, strenuous exercise, water immersion, or the weightless conditions of space flights.

Loeppky, J. A.↗

A helium-3/helium-4 dilution cryocooler for operation in zero gravity

This research effort covered the development of He-3/He-4 dilution cryocooler cycles for use in zero gravity. The dilution cryocooler is currently the method of choice for producing temperatures below 0.3 Kelvin in the laboratory. However, the current dilution cryocooler depends on gravity for their operation, so some modification is required for zero gravity operation. In this effort, we have demonstrated, by analysis, that the zero gravity dilution cryocooler is feasible. We have developed a cycle that uses He-3 circulation, and an alternate cycle that uses superfluid He-4 circulation. The key elements of both cycles were demonstrated experimentally. The development of a true 'zero-gravity' dilution cryocooler is now possible, and should be undertaken in a follow-on effort.

Hendricks, John B.↗

Measurement of engine-oil fuel dilution using laser induced florescence spectroscopy

An optical diagnostic, based on laser-induced fluorescence (LIF), has been developed for on-engine measurements of real-time fuel dilution of engine oil, or fuel in oil (FiO). Fuel dilution of oil is believed to be one of the underlying mechanisms that promotes low speed pre-ignition (LSPI) during high-load engine operations. While standard (e.g., ASTM D3524-90) methods are not capable of transient measurements, the LIF technique resolves transient dilution on the minutes time scale, making it possible to study the relation between FiO and LSPI. The measurement is based on adding a dye (ca. 500 ppm) to the fuel and monitoring for its presence in the oil via LIF. The instrument contains a 532-nm laser diode, and a spectrometer to resolve the LIF spectra. A fiber-optic assembly links the instrument to the engine measurement location; the probe is in a Y-configuration with the six fibers around one on a common probe end that connects to the engine; the Y-assembly legs are connected to the instrument; the two legs are the six fibers for transporting the laser light, and the single fiber for the fluorescence. We have expanded on our previous work (Parks et al, SAE paper 2007-01-4108, 2007), by demonstrating the diagnostic technique with to measure transient oil dilution on a 2.0-liter GM ECOTEC LNF single cylinder SI engine. The proposed LIF diagnostic will be critical in studying oil-dilution correlation with LSPI events.

Neupane, Sneha↗

Electrical injection and transport in Teflon-diluted hole transport materials

Diluting small molecule organic semiconductor hole transport materials with Teflon AF (TAF) dramatically increases their thermal/morphological stability while counterintuitively also increasing the current density in hole-only diodes. Here, we explore the origin of this current enhancement in co-evaporated blends of TAF and N,N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPD) and find that it results from improved hole injection and not from a mobility enhancement due to semiconductor dilution effects. Whereas electroabsorption measurements indicate that an interface dipole shift of up to 0.5 eV (depending on TAF concentration) aides hole injection at the indium-tin-oxide anode, time-of-flight and temperature-dependent current-voltage measurements show that the mobility of 25 vol% TAF:NPD blends decreases by roughly an order of magnitude relative to neat NPD despite having slightly lower energetic disorder. For comparison, diluting with 25 vol% high density polyethylene achieves a similar reduction in energetic disorder but only decreases the mobility by a factor of two. Furthermore, these results highlight the tradeoff between reducing energetic disorder and frustrating percolation in diluted organic semiconductors, and represent a step toward thermally-evaporated polymer-small molecule composites that maintain high mobility while offering improved morphological stability and lower refractive index for organic light emitting diodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗