Dimethylammonium Addition to Halide Perovskite Precursor Increases Vertical and Lateral Heterogeneit
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Jariwala, Sarthak↗
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Evaluation of the Interference of Tenax®TA Adsorbent With Dimethylformamide Dimethyl Acetal Reagent for Gas Chromatography-Dragonfly Mass Spectrometry and Future Gas Chromatography-Mass Spectrometry in Situ Analysis
Among future space missions, national aeronautics and space administration (NASA) selected two of them to analyze the diversity in organic content within Martian and Titan soil samples using a gas chromatograph – mass spectrometer (GC–MS) instrument. The Dragonfly space mission is planned to be launched in 2027 to Titan's surface and explore the Shangri-La surface region for years. One of the main goals of this mission is to understand the past and actual abundant prebiotic chemistry on Titan, which is not well characterized yet. The ExoMars space mission is planned to be launched in 2028 to Mars’ surface and explore the Oxia Planum and Mawrth Vallis region for years. The main objectives focus on the exploration of the subsurface soil samples, potentially richer in organics, that might be relevant for the search of past life traces on Mars where irradiation does not impact the matrices and organics. One recently used sample pre-treatment for gas chromatography – mass spectrometry analysis is planned on both space missions to detect refractory organic molecules of interest for astrobiology. This pre-treatment is called derivatization and uses a chemical reagent – called dimethylformamide dimethyl acetal (DMF-DMA) – to sublimate organic compounds keeping them safe from thermal degradation and conserving the chirality of the molecules extracted from Titan or Mars’ matrices. Indeed, the detection of building blocks of life or enantiomeric excess of some organics (e.g. amino acids) after DMF-DMA pre-treatment and GC–MS analyses would be both bioindicators. The main results highlighted by our work on DMF-DMA and Tenax®TA interaction and efficiency to detect organic compounds at ppb levels in a fast and single preparation are first that Tenax®TA did not show the onset of degradation until after 150 experiments – a 120 h at 300 °C experiment – which greatly exceeds the experimental lifetimes for the DraMS and GC-space in situ investigations. Tenax®TA polymer and DMF-DMA produce many by-products (about 70 and 46, respectively, depending on the activation temperature). Further, the interaction between the two leads to the production of 22 additional by-products from DMF-DMA degradation, but these listed by-products do not prevent the detection of trace-level organic molecules after their efficient derivatization and volatilization by DMF-DMA in the oven ahead the GC–MS trap and column.
DraMS-Dragonfly mission↗
Expanding the Cage of 2D Bromide Perovskites by Large A-Site Cations
Two-dimensional (2D) halide perovskites have outstanding optoelectronic properties, and they feature a variety of organic cation spacers and cage A-site cations that can be incorporated into their structures. It has recently been reported that the Goldschmidt tolerance factor can be relaxed and expanded in iodide 2D perovskites. Bromide 2D perovskites, whose multilayer structures and optical properties are much less studied, provide a great platform for studying structure-property relationships for 2D perovskites with large Asite cations. Herein, we report the synthesis and structure of three new 2D bromide perovskites-(BA)(2)(MHy)(2)Pb3Br10 (BA, butylammonium; MHy, methylhydrazinium), (BA)(2)(EA)(2)Pb3Br10 (EA is ethylammonium), and (BA)(2)(DMA)Pb2Br7 (DMA is dimethylammonium). We compared them with other 2D perovskites with different A-site cations but with the same spacer and layer thickness. Single-crystal structures show that the Pb-Br bonds are elongated to accommodate the large A-site cations. Additionally, the octahedra in (BA)(2)(MHy)(2)Pb3Br10 and (BA)(2)(EA)(2)Pb3Br10 are highly distorted, and their different stacking patterns of the inner and outer layers lead to the formation of the n = 3 phases. Density functional theory calculations show that 2D perovskites with larger A-site cations (e.g., DMA, MHy, and EA) have smaller band dispersions and larger effective masses than those with Cs+ and MA. (BA)(2)(MHy)(2)Pb3Br10 also exhibits one of the largest Rashba splittings in the literature. Structures with large cage cations also exhibit high band gaps within the same n number and short photoluminescence (PL) lifetimes. Temperature- and power-dependent PL measurements reveal that the broad shoulder in the PL peak originates from the trap states.
Emission↗
Altering the localization and toxicity of arsenic in rice grain
Previous work has shown that inorganic As localizes in rice bran whereas DMA localizes in the endosperm, but less is known about co-localization of As and S species and how they are affected by growing conditions. We used high-resolution synchrotron X-ray fluorescence imaging to image As and S species in rice grain from plants grown to maturity in soil (field and pot) and hydroponically (DMA or arsenite dosed) at field-relevant As concentrations. In hydroponics, arsenite was localized in the ovular vascular trace (OVT) and the bran while DMA permeated the endosperm and was absent from the OVT in all grains analyzed, and As species had no affect on S species. In pot studies, soil amended with Si-rich rice husk with higher DMA shifted grain As into the endosperm for both japonica and indica ecotypes. In field-grown rice from low-As soil, As localized in the OVT as arsenite glutathione, arsenite, and DMA. Results support a circumferential model of grain filling for arsenite and DMA and show Si-rich soil amendments alter grain As localization, potentially lessening risk to rice consumers.
59 BASIC BIOLOGICAL SCIENCES↗
Significant contributions of trimethylamine to sulfuric acid nucleation in polluted environments
Abstract As one of the least understood aerosol processes, nucleation can be a dominant source of atmospheric aerosols. Sulfuric acid (SA)-amine binary nucleation with dimethylamine (DMA) has been recognized as a governing mechanism in the polluted continental boundary layer. Here we demonstrate the importance of trimethylamine (TMA) for nucleation in the complex atmosphere and propose a molecular-level SA-DMA-TMA ternary nucleation mechanism as an improvement upon the conventional binary mechanism. Using the proposed mechanism, we could connect the gaseous amines to the SA-amine cluster signals measured in the atmosphere of urban Beijing. Results show that TMA can accelerate the SA-DMA-based new particle formation in Beijing by 50–100%. Considering the global abundance of TMA and DMA, our findings imply comparable importance of TMA and DMA to nucleation in the polluted continental boundary layer, with probably higher contributions from TMA in polluted rural environments and future urban environments with controlled DMA emissions.
54 ENVIRONMENTAL SCIENCES↗
3002 Humidified Tandem Differential Mobility Analyzer (HTDMA) Instrument Handbook
The Brechtel Manufacturing Inc. (BMI) Humidified Tandem Differential Mobility Analyzer (HT-DMA Model 3002) (Brechtel and Kreidenweis 2000a,b, Henning et al. 2005, Xerxes et al. 2014) measures how aerosol particles of different initial dry sizes grow or shrink when exposed to changing relative humidity (RH) conditions. It uses two different mobility analyzers (DMA) and a humidification system to make the measurements. One DMA selects a narrow size range of dry aerosol particles, which are exposed to varying RH conditions in the humidification system. The second (humidified) DMA scans the particle size distribution output from the humidification system. Scanning a wide range of particle sizes enables the second DMA to measure changes in size or growth factor (growth factor = humidified size/dry size), due to water uptake by the particles. A Condensation Particle Counter (CPC) downstream of the second DMA counts particles as a function of selected size in order to obtain the number size distribution of particles exposed to different RH conditions.
54 ENVIRONMENTAL SCIENCES↗
The Role of Dimethylammonium in Bandgap Modulation for Stable Halide Perovskites
Halide perovskites with bandgaps of 1.70–1.85 eV are of interest for multijunction photovoltaics. Mixing halides on the X site of the ABX3-structured perovskite system is a common way to reach these bandgaps, but this method introduces phase segregation pathways, limiting photovoltage. Recently, a new strategy for increasing the bandgap has been introduced, where cations normally too large to fit into the lattice, but compensated by smaller cations, are substituted on the A site. The mechanism underlying the increase of the bandgap with this strategy remained an open question. Here, we show that by partial substitution of the large dimethylammonium (DMA) cation at the A site of FA x Cs 1–x PbI y Br 3–y perovskites, a bandgap increase is observed not only when DMA is compensated by smaller Cs cations but also when only DMA is added, which is accompanied by an expansion of the crystal lattice. Our experimental findings suggest that adding DMA is causing an unexpected tilt in the perovskite octahedra, increasing the bandgap. Efficient solar cells based on 1.73 eV DMA-incorporated materials are extremely stable, retaining 96% of their original efficiency over 2200 h at 85 °C in the dark and 92% of their original efficiency after operation at 60 °C for 500 h. Finally, this octahedral tilting strategy is a promising route for attaining efficient and stable wide bandgap perovskite solar cells.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A dynamic parameterization of sulfuric acid–dimethylamine nucleation and its application in three-dimensional modeling
Sulfuric acid (SA) is a governing gaseous precursor for atmospheric new particle formation (NPF), a major source of global ultrafine particles, in environments studied around the world. In polluted urban atmospheres with high condensation sinks (CSs), the formation of stable SA–amine clusters, such as SA–dimethylamine (DMA) clusters, usually initializes intense NPF events. Coagulation scavenging and cluster evaporation are dominant sink processes of SA–amine clusters in urban atmospheres, yet these loss processes are not quantitatively included in the present parameterizations of SA–amine nucleation. We herein report a parameterization of SA–DMA nucleation, based on cluster dynamic simulations and quantum chemistry calculations, with certain simplifications to greatly reduce the computational costs. Compared with previous SA–DMA nucleation parameterizations, this new parameterization was able to reproduce the dependences of particle formation rates on temperature and CSs. We then incorporated it in a three-dimensional (3-D) chemical transport model to simulate the evolution of the particle number size distributions. Simulation results showed good consistency with the observations in the occurrence of NPF events and particle number size distributions in wintertime Beijing and represented a significant improvement compared to that using a parameterization without coagulation scavenging. Quantitative analysis shows that SA–DMA nucleation contributes significantly to nucleation rates and aerosol population during the 3-D simulations in Beijing (>99 % and >60 %, respectively). These results broaden the understanding of NPF in urban atmospheres and stress the necessity of including the effects of coagulation scavenging and cluster stability in simulating SA–DMA nucleation in 3-D simulations. Representing these processes is thus likely to improve model performance in particle source apportionment and quantification of aerosol effects on air quality, human health, and climate.
Li, Yuyang↗
Cluster-dynamics-based parameterization for sulfuric acid–dimethylamine nucleation: comparison and selection through box and three-dimensional modeling
Clustering of gaseous sulfuric acid (SA) enhanced by dimethylamine (DMA) is a major mechanism for new particle formation (NPF) in polluted atmospheres. However, uncertainty remains regarding the SA–DMA nucleation parameterization that reasonably represents cluster dynamics and is applicable across various atmospheric conditions. This uncertainty hinders accurate three-dimensional (3-D) modeling of NPF and the subsequent assessment of its environmental and climatic impacts. Here we extensively compare different cluster-dynamics-based parameterizations for SA–DMA nucleation and identify the most reliable one through a combination of box model simulations, 3-D modeling, and in situ observations. Results show that the parameterization derived from Atmospheric Cluster Dynamic Code (ACDC) simulations, incorporating the latest theoretical insights (DLPNO-CCSD(T)/aug-cc-pVTZ//ωB97X-D/6-311++G(3df,3pd) level of theory) and adequate representation of cluster dynamics, exhibits dependable performance in 3-D NPF simulation for both winter and summer conditions in Beijing and shows promise for application in diverse atmospheric conditions. Another ACDC-derived parameterization, replacing the level of theory with RI-CC2/aug-cc-pV(T+d)Z//M06-2X/6–311++G(3df,3pd), also performs well in NPF modeling at relatively low temperatures around 280 K but exhibits limitations at higher temperatures due to inappropriate representation of SA–DMA cluster thermodynamics. Additionally, a previously reported parameterization incorporating simplifications is applicable for simulating NPF in polluted atmospheres but tends to overestimate particle formation rates under conditions of elevated temperature (>∼300 K) and low-condensation sink (<∼3×10 -3 s −1 ). Our findings highlight the applicability of the new ACDC-derived parameterization, which couples the latest SA–DMA nucleation theory and holistic cluster dynamics, in 3-D NPF modeling. The ACDC-derived parameterization framework provides a valuable reference for developing parameterizations for other nucleation systems.
Shen, Jiewen↗
Nitrile/Buna N Material Failure Assessment for an O-Ring used on the Gaseous Hydrogen Flow Control Valve (FCV) of the Space Shuttle Main Engine
After the rollout of Space Shuttle Discovery in April 2005 in preparation for return-to-flight, there was a failure of the Orbiter (OV-103) helium signature leak test in the gaseous hydrogen (GH2) system. Leakage was attributed to the Flow Control Valve (FCV) in Main Engine 3. The FCV determined to be the source of the leak for OV-103 is designated as LV-58. The nitrile/Buna N rubber O-ring seal was removed from LV-58, and failure analysis indicated radial cracks providing leak paths in one quadrant. Cracks were eventually found in 6 of 9 FCV O-rings among the three Shuttle Orbiters, though none were as severe as those for LV-58, OV-103. Testing by EM10 at MSFC on all 9 FCV O- rings included: laser dimensional, Shore A hardness and properties from a dynamic mechanical analyzer (DMA) and an Instron tensile machine. The following test data was obtained on the cracked quadrant of the LV-58, OV-103 O-ring: (1) the estimated compression set was only 9.5%, compared to none for the rest of the O-ring; (2) Shore A hardness for the O.D. was higher by almost 4 durometer points than for the rest of the O-ring; and (3) DMA data showed that the storage/elastic modulus E was almost 25% lower than for the rest of the O-ring. Of the 8 FCV O-rings tested on an Instron, 4 yielded tensile strengths that were below the MIL spec requirement of 1350 psi-a likely influence of rubber cracking. Comparisons were made between values of modulus determined by DNA (elastic) and Instron (Young s). Each nitrile/Buna N O-ring used in the FCV conforms to the MIL-P-25732C specification. A number of such O-rings taken from shelf storage at MSFC and Kennedy Space Center (KSC) were used to generate a reference curve of DMA glass transition temperature (Tg) vs. shelf storage time ranging from 8 to 26 years. A similar reference curve of TGA onset temperature (of rubber weight loss) vs. shelf storage time was also generated. The DMA and TGA data for the used FCV O-rings were compared to the reference curves. Correlations were also made between the DMA modulus (at 22 C) and Shore A hardness for all 9 of the FCV O-rings used among the three Shuttle Orbiters. The radial cracking in the FCV O-rings was determined to be due to ozone attack, as nitrile/Buna N rubber is susceptible to such attack. Nitrile/Buna N material under MIL-P25732C should be used in a hydraulic fluid environment to help protect it from cracking. However, the FCV O-rings were used in an air only environment. The FCV design has as much as a 9-mil gap that allows the O.D. of the O-ring to be directly exposed to ozone, pressurized air and some elevated temperatures, accelerating the weathering process that leads to O-ring cracking. Space Shuttle flights will likely not continue past 2010. Therefore, Shuttle management decided to continue using the nitrile/Buna N material for the FCVs, but have each O-ring replaced after 3 years to minimize any chances for crack initiation.
Wingard, Doug↗
Computational Aerothermal Modeling and Simulation of Hypersonic, Low-density Flows for the ADEPT Drag Modulated Aerocapture Mission
NASA Ames Entry Systems and Technology Division has been leading development and testing of the Adaptable, Deployable, Entry and Placement Technology (ADEPT). A teaming partnership with JPL has been established to study and develop a compelling application of the ADEPT mechanically deployable hypersonic decelerator as part of the Venus Drag Modulated Aerocapture (VDMA) JPL R&TD effort. The primary work of this activity is to develop a design tool for the ADEPT drag skirt (e.g. a CFD-anchored CBAERO model) that enables rapid estimation of aerothermal environments for a range of candidate trajectories. This capability will enable rapid feasibility trades and design assessments for early stage mission concept evaluation for ADEPT Drag Modulated Aerocapture applications. Results of using TPSizer provided an ADEPT carbon fabric design thickness of the required number of fabric layers needed for predicted aerothermal environments and still have sufficient fabric remaining for overall vehicle integrity. This resulted in aerothermal design closure of the ADEPT drag skirt. In addition, the similar methodology for Venus DMA was used to assess a similar DMA operation at Earth as part of a possible Technology Demonstration Mission (TDM) for ADEPT DMA. This analysis showed that there is a close similarity of design approaches for an Earth DMA TDM that would be applicable to Venus DMA mission designs.
Drag Modulated Aerocapture↗
Total Mercury Analysis of Radioactive Waste Containing Multiple Mercury Species
In this work, a direct mercury analyzer (DMA) was used to analyze total mercury in radioactive waste samples containing methylmercury and other forms of mercury including Hg o (elemental) together with inorganic ionic mercury species and complexes. These samples were also analyzed using Cold Vapor Atomic Absorption Spectroscopy (CVAAS) and/or Inductively Coupled Plasma Mass Spectroscopy (ICMS). Comparative statistical evaluation of the results from spike solutions/simulants, liquid radioactive waste samples, and interlaboratory performance test samples demonstrated that the various methods generated accurate and/or equivalent total mercury data and equivalent precision (2σ ± < 20%). Triplicate total mercury analysis of an exemplar radioactive waste resulted in an average value of 54.1 mg/L (as Hg) using CVAAS, 55.1 mg/L using ICPMS and 56.0 mg/L using DMA. A primary advantage of the DMA in a radioactive environment is avoiding multi-step, labor-intensive, time-consuming and waste-producing sample preparation protocols needed for CVAAS and ICPMS. DMA was determined to be the preferred method for measuring total mercury in the Savannah River National Laboratory (SRNL) radioanalytical laboratory based on analytical performance combined with ease of use in a radiological containment unit.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Multiple-charging effects on the CCN activity and hygroscopicity of surrogate black carbon particles
Accurate measurements of cloud condensation nuclei (CCN) activity and hygroscopicity of black carbon (BC)-containing particles are particularly important because of the positive climate forcing from these particles. Such measurements are typically conducted on particles selected by a Differential Mobility Analyzer (DMA), which in addition to singly charged particles transmits multiply charged larger particles that have the same electrical mobility. These larger particles activate at lower supersaturations than the singly charged particles, biasing measurements and resulting in overestimation of CCN activity and hygroscopicity parameter (κ). Here, we measure the CCN activity and determine κ for different BC surrogates with electrical mobility diameters from 100 to 200 nm selected 1) only by electrical mobility with a DMA, and 2) by both electrical mobility and mass using a DMA and a Centrifugal Particle Mass Analyzer (CPMA), thus allowing selection of only singly charged particles. We demonstrate the use of the DMA-CPMA system in resolving biases caused by multiply charged particles, and we show that the effect of multiple charging on the CCN activity of the BC particles is strongly influenced by morphology dispersion, i.e., the variability due to the range of morphologies of particles that have the same electrical mobility and mass. Finally, our findings show that electrical mobility-based methods alone are unlikely to lead to accurate results in measurements of CCN activation and hygroscopicity of BC particles, even for those with a more compact morphology.
54 ENVIRONMENTAL SCIENCES↗
Axial vs equatorial: Capturing the intramolecular charge transfer state geometry in conformational polymorphic crystals of a donor–bridge–acceptor dyad in nanosecond-time-scale
Two conformational polymorphs of a donor–bridge–acceptor (D-B-A) dyad, p-(CH 3 ) 2 N-C 6 H 4 -(CH 2 ) 2 -(1-pyrenyl)/PyCHDMA, were studied, where the electron donor (D) moiety p-(CH 3 ) 2 N-C 6 H 4 /DMA is connected through a bridging group (B), –CH 2 –CH 2 –, to the electron acceptor (A) moiety pyrene. Though molecular dyads like PyCHDMA have the potential to change solar energy into electrical current through the process of photoinduced intramolecular charge transfer (ICT), the major challenge is the real-time investigation of the photoinduced ICT process in crystals, necessary to design solid-state optoelectronic materials. The time-correlated single photon counting (TCSPC) measurements with the single crystals showed that the ICT state lifetime of the thermodynamic form, PyCHDMA1 (pyrene and DMA: axial), is ~3 ns, whereas, for the kinetic form, PyCHDMA20 (pyrene and DMA: equatorial), it is ~7 ns, while photoexcited with 375 nm radiation. The polymorphic crystals were photo-excited and subsequently probed with a pink Laue x-ray beam in time-resolved x-ray diffraction (TRXRD) measurements. The TRXRD results suggest that in the ICT state, due to electron transfer from the tertiary N-atom in DMA moiety to the bridging group and pyrene moiety, a decreased repulsion between the lone-pair and the bond-pair at N-atom induces planarity in the C–N–(CH 3 ) 2 moiety, in both polymorphs. The Natural Bond Orbital calculations and partial atomic charge analysis by Hirshfeld partitioning also corroborated the same. Although the interfragment charge transfer (IFCT) analysis using the TDDFT results showed that for the charge transfer excitation in both conformers, the electrons were transferred from the DMA moiety to mostly the pyrene moiety, the bridging group has little role to play in that.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Effect of Humidity on the Reactive Uptake of Ammonia and Dimethylamine by Nitrogen-Containing Secondary Organic Aerosol
This study investigated the uptake of ammonia (NH3) by secondary organic aerosol (SOA) particles generated via limonene photooxidation or ozonolysis as well as the uptake of dimethylamine (DMA) by limonene ozonolysis, α-cedrene photooxidation, or toluene photooxidation SOA in an environmental chamber between 0–50% relative humidity. In addition to the acid-base equilibrium uptake, NH3 and DMA can react with SOA carbonyl compounds converting them into nitrogen-containing organic compounds (NOCs). The effective reactive uptake coefficients for the formation of NOCs from ammonia were measured on the order of 10−5. The observed DMA reactive uptake coefficients ranged from 10−5 to 10−4. Typically, the reactive uptake coefficient decreased with increasing relative humidity. This is consistent with NOC formation by a condensation reaction between NH3 or DMA with SOA, which produces water as a product. Ammonia is more abundant in the atmosphere than amines. However, the larger observed reactive uptake coefficient suggests that amine uptake may also be a potential source of organic nitrogen in particulate matter.
54 ENVIRONMENTAL SCIENCES↗
Comparison of manually produced and automated cross country movement maps using digital image processing techniques
The Image-Based Information System (IBIS) was used to automate the cross country movement (CCM) mapping model developed by the Defense Mapping Agency (DMA). Existing terrain factor overlays and a CCM map, produced by DMA for the Fort Lewis, Washington area, were digitized and reformatted into geometrically registered images. Terrain factor data from Slope, Soils, and Vegetation overlays were entered into IBIS, and were then combined utilizing IBIS-programmed equations to implement the DMA CCM model. The resulting IBIS-generated CCM map was then compared with the digitized manually produced map to test similarity. The numbers of pixels comprising each CCM region were compared between the two map images, and percent agreement between each two regional counts was computed. The mean percent agreement equalled 86.21%, with an areally weighted standard deviation of 11.11%. Calculation of Pearson's correlation coefficient yielded +9.997. In some cases, the IBIS-calculated map code differed from the DMA codes: analysis revealed that IBIS had calculated the codes correctly. These highly positive results demonstrate the power and accuracy of IBIS in automating models which synthesize a variety of thematic geographic data.
Wynn, L. K.↗
Thermal Protection System to Enable Ice Giant Aerocapture Mission for Delivering Both an Orbiter and an In Situ Probe
The Ice Giants have been identified as high priority science destinations in the last Decadal Survey [1] and could benefit from aerocapture as the primary method for orbit insertion [2]. A mass-efficient aerocapture system will enable the delivery of an orbiter along with an atmospheric probe (for in situ measurements to anchor global data collected by the orbiter) and possibly a lander at Triton [3]. Aerocapture could be executed either using low L/D rigid aeroshell with lift modulation (LMA) [4] or using deployable aeroshell using drag modulation (DMA) [3]. Nearly two decades ago, a NASA-funded team performed Neptune-Triton aerocapture studies with a mid-L/D lifting configuration [5] for achieving orbit using LMA. This study showed aerocapture challenges. Due to very high peak entry conditions combined with very high heat-load, a suite of TPS materials was required and this suite was deemed problematic from a qualification perspective, due test facility limitations. In the past 20 years, progress made in GN&C for lift-guided entry missions such as MSL, Orion EFT1, Mars 2020 and the upcoming Artemis missions, and the expertise in blunt body aerodynamics at large scale (~ 5m) has led the EDL community to conclude that aerocapture is a “go do” engineering activity and most technologies are in hand to propose missions with aerocapture [6] [7]. Aerocapture using DMA, currently in development, is an option for Ice Giant Missions. While DMA is simpler in some sense, due to ballistic entry and no need for lift-guided maneuvering, it has challenges and it’s maturity is lower. LMA and DMA both require one or more ablative Thermal Protection System (TPS) materials for the rigid aeroshell element. The ablative TPS needs to be robust and mass efficient due to the high heat loads and size of the rigid aeroshell. Currently, there are capable ablative thermal protection materials, e.g., Heatshield for Extreme Entry Environments Technology (HEEET), 3-D woven Mid-Density Carbon- Phenolic (3MDCP), and PICA (Phenolic-Impregnated Carbon Ablator) that are mature, i.e., at TRL 6 or higher. NASA also invested in Conformal PICA that was matured to TRL 5. Our goal is to evaluate the applicability of high TRL TPS and consider other design options. We first establish bounding aerocapture trajectories for a wide range of arrival conditions and the associated aerothermal environment. Based on the environments, we then determine the predicted TPS mass for the aeroshell [4]. In this presentation, we will outline the process by which we establish bounding aerocapture trajectories for hyperbolic excess velocities ranging from 27 km/s to 35 km/s, which are shown to be a range of velocities that can reduce the trip time from ~14 years to 8 years. The above velocity range translates to ~12 km/s to ~24 km/s arrival velocities at the planetary entry interface [2]. The velocity reduction required to achieve orbit ranges between ~2.5 km/s to 9.5 km/s for both Neptune and Triton. Propulsive insertion alone, due to the amount of fuel required to achieve the required velocity reduction, limits the science returned [2]. We establish the bounding aerocapture trajectories for a low L/D (~ 0.4) configuration for three different ballistic coefficients. The ballistic coefficient range is determined from three different aeroshell diameters of 3m, 4m and 5m and with an entry system mass of 2200 kg. With the above range of design parameters, we then determine conservative/bounding estimates of aerothermal environments by using a combination of CFD simulations and stagnation point heating estimates [7]. This engineering approach allows us to first assess the TPS need vs. TPS capability and determine the applicability of existing TPS. Once an applicable suite of TPS is determined, the TPS thickness and mass are computed. We show that the TPS mass fraction can be as low as 5% to as high as 20%, depending on total trip time reduction and other design parameters for a range of TPS. This is a large range for TPS mass fraction. We show PICA and HEEET can indeed enable aerocapture missions, but the missions incur a mass penalty. TPS mass savings, can be further reduced with the use of conformal PICA. Advancing the development of Conformal PICA to make it robust across the entire aerothermal environment (peak heat-flux, pressure and shear) range will result in TPS mass fractions of < 10% for Ice Giant aerocapture missions such as the Neptune-Triton mission. Aerocapture allows for not only shortening the trip time but enables larger mass to be placed in orbit. Furthermore, probes deployed from orbit will benefit in reduced entry environments allowing for a lower risk TPS implementation as compared to mission designs where the probe is released prior to orbit insertion. One of the challenges for the Ice Giant community is to ensure mission designs that maximize science and allow flexibility in the placement of the entry probe. The traditional approach to release the probe ahead of the orbiter may not optimize returned science. In this presentation, we will make the case for mature TPS such as HEEET and PICA. While these materials can enable aerocapture missions, completing the development of conformal PICA and extending Conformal PICA to be more robust, will have significant impact to TPS mass efficiency and significantly enhance science return for future Gas- and Ice-Giant missions.
E Venkatapathy↗
Particle_hygroscopicity_growth_factor_HFIMS_TRACER_2022_HOUSTON_IOP
This dataset contains high-temporal-resolution measurements of hygroscopic growth factors (GF), and instrument diagnostic/environmental parameters collected during the TRACER campaign using a coupled Differential Mobility Analyzer (DMA) and Fast Integrated Mobility Spectrometer (FIMS) system (HFIMS). The dataset consists of 49,645 time steps and covers 20 discrete growth factor bins (FIMS_GFbinc). The primary data product is the Probability Density Function (FIMS_cPDF), which characterizes aerosol hygroscopic growth behavior under controlled relative humidity conditions. Instrument operational parameters, including flow temperatures, relative humidities, pressures, and counts for both DMA and FIMS, are provided for quality assurance.
DMA_Dp_mean↗