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At least 145 records · Page 8

Solid Hydrogen Experiments for Atomic Propellants

This paper illustrates experiments that were conducted on the formation of solid hydrogen particles in liquid helium. Solid particles of hydrogen were frozen in liquid helium, and observed with a video camera. The solid hydrogen particle sizes, their molecular structure transitions, and their agglomeration times were estimated. article sizes of 1.8 to 4.6 mm (0.07 to 0. 18 in.) were measured. The particle agglomeration times were 0.5 to 11 min, depending on the loading of particles in the dewar. These experiments are the first step toward visually characterizing these particles, and allow designers to understand what issues must be addressed in atomic propellant feed system designs for future aerospace vehicles.

Palaszewski, Bryan↗

An Agent-Based Model of New Venture Creation: Conceptual Design for Simulating Entrepreneurship

There is a growing debate over the means by which regions can foster the growth of entrepreneurial activity in order to stimulate recovery and growth of their economies. On one side, agglomeration theory suggests the regions grow because of strong clusters that foster knowledge spillover locally; on the other side, the entrepreneurial action camp argues that innovative business models are generated by entrepreneurs with unique market perspectives who draw on knowledge from more distant domains. We will show you the design for a novel agent-based model of new venture creation that will demonstrate the relationship between agglomeration and action. The primary focus of this model is information exchange as the medium for these agent interactions. Our modeling and simulation study proposes to reveal interesting relationships in these perspectives, offer a foundation on which these disparate theories from economics and sociology can find common ground, and expand the use of agent-based modeling into entrepreneurship research.

Provance, Mike↗

Estimating the Rate of Occurrence of Renal Stones in Astronauts

Changes in urine chemistry, during and post flight, potentially increases the risk of renal stones in astronauts. Although much is known about the effects of space flight on urine chemistry, no inflight incidence of renal stones in US astronauts exists and the question "How much does this risk change with space flight?" remains difficult to accurately quantify. In this discussion, we tackle this question utilizing a combination of deterministic and probabilistic modeling that implements the physics behind free stone growth and agglomeration, speciation of urine chemistry and published observations of population renal stone incidences to estimate changes in the rate of renal stone presentation. The modeling process utilizes a Population Balance Equation based model developed in the companion IWS abstract by Kassemi et al. (2016) to evaluate the maximum growth and agglomeration potential from a specified set of urine chemistry values. Changes in renal stone occurrence rates are obtained from this model in a probabilistic simulation that interrogates the range of possible urine chemistries using Monte Carlo techniques. Subsequently, each randomly sampled urine chemistry undergoes speciation analysis using the well-established Joint Expert Speciation System (JESS) code to calculate critical values, such as ionic strength and relative supersaturation. The Kassemi model utilizes this information to predict the mean and maximum stone size. We close the assessment loop by using a transfer function that estimates the rate of stone formation from combining the relative supersaturation and both the mean and maximum free stone growth sizes. The transfer function is established by a simulation analysis which combines population stone formation rates and Poisson regression. Training this transfer function requires using the output of the aforementioned assessment steps with inputs from known non-stone-former and known stone-former urine chemistries. Established in a Monte Carlo system, the entire renal stone analysis model produces a probability distribution of the stone formation rate and an expected uncertainty in the estimate. The utility of this analysis will be demonstrated by showing the change in renal stone occurrence predicted by this method using urine chemistry distributions published in Whitson et al. 2009. A comparison to the model predictions to previous assessments of renal stone risk will be used to illustrate initial validation of the model.

gravitational physiology↗

Coupled CFD-PBE Predictions of Renal Stone Size Distributions in the Nephron in Microgravity

In this paper, a deterministic model is developed to assess the risk of critical renal stone formation for astronauts during space travel. A Population Balance Equation (PBE) model is used to compute the size distribution of a population of nucleating, growing and agglomerating renal calculi as they are transported through different sections of the nephron. The PBE model is coupled to a Computational Fluid Dynamics (CFD) model that solves for steady state flow of urine and transport of renal calculi along with the concentrations of ionic species, calcium and oxalate, in the nephron using an Eulerian two-phase mathematical framework. Parametric simulation are performed to study stone size enhancement and steady state volume fraction distributions in the four main sections of the nephron under weightlessness conditions. Contribution of agglomeration to the stone size distribution and effect of wall friction on the stone volume fraction distributions are carefully examined. Case studies using measured astronaut urinary calcium and oxalate concentrations in microgravity as input indicate that under nominal conditions the largest stone sizes developed in Space will be still considerably below the critical range for problematic stone development. However, results also indicate that the highest stone volume fraction occurs next to the tubule and duct walls. This suggests that there is an increased potential for wall adhesion with the possibility of evolution towards critical stone sizes.

Microgravity↗

Coupled CFD-PBE Predictions of Renal Stone Size Distributions in the Nephron in Microgravity

In this paper, a deterministic model is developed to assess the risk of critical renal stone formation for astronauts during space travel. A Population Balance Equation (PBE) model is used to compute the size distribution of a population of nucleating, growing and agglomerating renal calculi as they are transported through different sections of the nephron. The PBE model is coupled to a Computational Fluid Dynamics (CFD) model that solves for steady state flow of urine and transport of renal calculi along with the concentrations of ionic species, calcium and oxalate, in the nephron using an Eulerian two-phase mathematical framework. Parametric simulation are performed to study stone size enhancement and steady state volume fraction distributions in the four main sections of the nephron under weightlessness conditions. Contribution of agglomeration to the stone size distribution and effect of wall friction on the stone volume fraction distributions are carefully examined. Case studies using measured astronaut urinary calcium and oxalate concentrations in microgravity as input indicate that under nominal conditions the largest stone sizes developed in Space will be still considerably below the critical range for problematic stone development. However, results also indicate that the highest stone volume fraction occurs next to the tubule and duct walls. This suggests that there is an increased potential for wall adhesion with the possibility of evolution towards critical stone sizes.

Crystal Growth↗

Cold Traps of Hypervolatiles in the Protosolar Nebula at the Origin of the Peculiar Composition of Comet C/2016 R2 (PanSTARRS)

Recent observations of the long-period comet C/2016 R2 (PanSTARRS; hereafter R2) indicate an unusually high N2/CO abundance ratio, typically larger than ∼0.05, and at least 2–3 times higher than the one measured in 67P/Churyumov–Gerasimenko. Another striking compositional feature of this comet is its heavy depletion in H2O (H2O/CO ∼ 0.32%), compared to other comets. Here we investigate the formation circumstances of a generic comet whose composition reproduces these two key features. We first envisage the possibility that this comet agglomerated from clathrates, but we find that such a scenario does not explain the observed low water abundance. We then alternatively investigate the possibility that the building blocks of R2 agglomerated from grains and pebbles made of pure condensates via the use of a disk model describing the radial transport of volatiles. We show that N2/CO ratios reproducing the value estimated in this comet can be found in grains condensed in the vicinity of the CO and N2 ice lines. Moreover, high CO/H2O ratios (>100 times the initial gas-phase value) can be found in grains condensed in the vicinity of the CO ice line. If the building blocks of a comet assembled from such grains, they should present N2/CO and CO/H2O ratios consistent with the measurements made in R2's coma. Our scenario indicates that R2 formed in a colder environment than the other comets that share more usual compositions. Our model also explains the unusual composition of the interstellar comet 2l/Borisov.

Olivier Mousis↗

The Spectral Characteristics of Lunar Agglutinates: Visible-Near-Infrared Spectroscopy of Apollo Soil Separates

The lunar surface evolves over time due to space weathering, and the visible–near-infrared spectra of more mature (i.e., heavily weathered) soils are lower in reflectance and steeper in spectral slope (i.e., darker and redder) than their immature counterparts. These spectral changes have traditionally been attributed to the space-weathered rims of soil grains (and particularly nanophase iron therein). However, understudied thus far is the spectral role of agglutinates—the agglomerates of mineral and lithic fragments, nanophase iron, and glass that are formed by micrometeoroid impacts and are ubiquitous in mature lunar soils. We separated agglutinates and non-agglutinates from six lunar soils of varying maturity and composition, primarily from the 125–250 μm size fraction, and measured their visible–near-infrared reflectance spectra. For each soil, the agglutinate spectra are darker, redder, and have weaker absorption bands than the corresponding non-agglutinate and unsorted soil spectra. Moreover, greater soil maturity corresponds to darker agglutinate spectra with weaker absorption bands. These findings suggest that agglutinates (rather than solely the space-weathered rims) play an important role in both the darkening and reddening of mature soils—at least for the size fractions examined here. Comparisons with analog soils suggest that high nanophase iron abundance in agglutinates is likely responsible for their low reflectance and spectrally red slope. Additional studies of agglutinates are needed both to more comprehensively characterize their spectral properties (across size fractions and in mixing with non-agglutinates) and to assess the relative roles of agglutinates and rims in weathering-associated spectral changes. Plain Language Summary - In scientific study of the Moon, one key focus is surface processes: how do physical and chemical properties of the Moon’s surface change over time due to weathering (e.g., bombardment by micrometeoroids and by particles from the Sun)? Such investigations provide valuable insights into the Moon’s history (such as the ages of impact craters) that are often deduced from measurements of reflected light; as a soil is weathered it reflects light differently, which manifests visually as a progressive darkening of the soil. This phenomenon had primarily been attributed to weathering-associated development of rims on individual soil grains, but in this work we explored an alternative cause: soil particles known as agglutinates (misshapen, vesicular agglomerates of mineral fragments, iron, and glass that form due to weathering processes). We isolated agglutinates of six soil samples from the Moon and measured how they reflect light. We find that they reflect light in patterns reminiscent of how the Moon’s surface does when weathered. These findings suggest that agglutinates play a more important role than previously thought in determining the light-reflecting properties of the Moon’s surface, thus warranting greater and more nuanced consideration in future studies of how the Moon’s surface changes over time.

spectroscopy↗

Modeling Heat Transfer and Reaction Kinetics of Biomass in Pyrolysis Feeding Systems

Biomass feedstocks can be used to produce low carbon-intensity chemicals and liquid fuels by displacing fossil-fuel sources. Pyrolysis is the thermal decomposition of biomass in the absence of oxygen and can be used to produce crude biofuels. A typical feeding mechanism for pyrolysis reactors is by lock hopper followed by a horizontal auger feeder. Particle agglomeration and plugging of the auger screw are regularly occurring phenomena that is detrimental to the process since it results in the need for periodic inspection and cleaning. The underlying mechanisms leading to agglomeration and plugging are unclear, but a working hypothesis is that heat from the reactor raises the temperature of the biomass in the feeder to the point at which preliminary decomposition reactions occur and produce "sticky" products. Using principles of heat and mass transfer, we derived one-dimensional differential equations for heat flow from the pyrolysis reactor through the auger feeder. Temperature profiles were solved from the system of one-dimensional differential equations using the shooting method. Subsequently, we used the temperature profiles as a one-way coupling to a reaction model for the biomass in the feeder. Kinetic models were adopted from the literature and used to predict the formation of intermediates, products, char, extractives, and metaplastics as well as phase changes along the auger feeder. Species were identified that correlated with softening of the biomass, causing it to become sticky and plug the feeder. We will discuss the details of this work, our findings, and the direction of future work that includes fully coupled transport and reaction-kinetics simulations.

BIOMASS FUELS↗

Influence of mixing on the generation of nanoparticles in cement systems

In this work, we study the effect of mixing intensity on the size and concentration of nanoparticles in quartz and cement systems. We vary the local shear rate in the studied suspensions induced by mixing by either changing solid volume fraction or mixing speed. Our results obtained on quartz, cement and quartz-cement suspensions provide a master curve relating the concentration of nanoparticles in the pore solution as a function of the local shearing conditions computed at a micromechanical level. Our results suggest, in accordance with literature, that high mixing intensity is at the origin of a detachment of nano-hydrates from the surface of cement particles. These nanoparticles can be stabilized and therefore detected in the pore-solution only in the presence of superplasticizers, which inhibit their agglomeration to other particles.

36 MATERIALS SCIENCE↗

Prehydration of calcium sulfoaluminate (CSA) clinker at different relative humidities

The use of CSA cement in practice has been hindered by its unstable performance and short shelf-life caused by the prehydration of CSA clinker. In this study, the effect of ambient humidity on the prehydration rate and process of CSA clinker was investigated. The prehydration degree, ageing progress, and the dynamic change of mineral composition of CSA clinker exposed to five different relative humidities (ranging from 23% to 98%) for up to 180 days were studied. Experiments revealed that the ambient humidity of 60% RH can be considered a threshold value for storage of CSA clinker. Exposure of CSA clinker to RH higher than 60% will not only result in a significant decrease of hydraulic reactivity, but also in agglomeration of the clinker. Although the exposure of CSA clinker to RH lower than 60% has little effect on the hydraulic reactivity, the main hydration peak was found to be slightly delayed with the increase of RH.

36 MATERIALS SCIENCE↗

Quantitative assessment of particle dispersion in polymeric composites and its effect on mechanical properties

In this work, an automated image analysis tool is developed to establish quantitative correlations between the particle/cluster size distribution and the mechanical properties of particle reinforced polymer composites (PRPC).This automated image analysis tool is developed within python programming software to process and analyze the microstructural images of the polymerbased composite materials. The spent coffee bean powder (SCBP) reinforced poly-propylene carbonate (PPC) polymer composite with differing wt.% of the filler is selected for the analysis. Detailed statistical analysis of the microstructural images reveals that ‘clustering of clusters’ is also presented in addition to the most commonly reported ‘clustering of particles’, and the distribution of particle/clusters is bimodal. Based on these findings, an effective volume fraction for the filler material is proposed to mainly capture the agglomeration effect. With this effective volume fraction, the standard rule-of-mixture model correctly captures the experimentally measured tensile strength and modulus as a function of filler wt.%. Further, the applicability of this effective volume fraction for other theoretical models is also analyzed. The detailed statistical analysis of the microstructure and the proposed effective volume fraction helps to develop a deeper quantitative understanding of the PRPC than the conventional qualitative correlation of microstructural features with the properties and failure processes.

36 MATERIALS SCIENCE↗

Genetically Controlled Iron Oxide Biomineralization in Encapsulin Nanocompartments for Magnetic Manipulation of a Mammalian Cell Line

Magnetic nanoparticles have proven invaluable for biomechanical investigations due to their ability to exert localized forces. However, cellular delivery of exogenous magnetic agents often results in endosomal entrapment, thereby limiting their utility for manipulating subcellular structures. This study characterizes and exploits fully genetically controlled biomineralization of iron-oxide cores inside encapsulin nanocompartments to enable magnetic-activated cell sorting (MACS) and magnetic cell manipulation. The fraction of MACS-retained cells showed substantial overexpression of encapsulins and exhibited both para- and ferrimagnetic responses with magnetic moments of 10 -15 A m 2 per cell, comparable to standard exogenous labels for MACS. Electron microscopy revealed that MACS-retained cells contained densely packed agglomerates of ≈30 nm iron oxide cores consisting of ultrafine quasicrystalline ordered nuclei within an amorphous matrix of iron, oxygen, and phosphorus. Scanning transmission X-ray microscopy, X-ray absorption spectroscopy, and Raman microspectroscopy confirmed that the iron-oxide species are consistent with ferric oxide (Fe 2 O 3 ). In addition, the encapsulin-overexpressing MACS-retained cells can be manipulated by a magnetic needle and regrown in patterns determined by magnetic gradients. This study demonstrates that the formation of quasicrystalline iron oxide with mixed para/ferrimagnetic behavior in the cytosol of mammalian cells enables magnetic manipulation without the delivery of exogenous agents.

60 APPLIED LIFE SCIENCES↗

Not All Aggregates Are Made the Same: Distinct Structures of Solution Aggregates Drastically Modulate Assembly Pathways, Morphology, and Electronic Properties of Conjugated Polymers

Abstract Tuning structures of solution‐state aggregation and aggregation‐mediated assembly pathways of conjugated polymers is crucial for optimizing their solid‐state morphology and charge‐transport property. However, it remains challenging to unravel and control the exact structures of solution aggregates, let alone to modulate assembly pathways in a controlled fashion. Herein, aggregate structures of an isoindigo–bithiophene‐based polymer (PII‐2T) are modulated by tuning selectivity of the solvent toward the side chain versus the backbone, which leads to three distinct assembly pathways: direct crystallization from side‐chain‐associated amorphous aggregates, chiral liquid crystal (LC)‐mediated assembly from semicrystalline aggregates with side‐chain and backbone stacking, and random agglomeration from backbone‐stacked semicrystalline aggregates. Importantly, it is demonstrated that the amorphous solution aggregates, compared with semicrystalline ones, lead to significantly improved alignment and reduced paracrystalline disorder in the solid state due to direct crystallization during the meniscus‐guided coating process. Alignment quantified by the dichroic ratio is enhanced by up to 14‐fold, and the charge‐carrier mobility increases by a maximum of 20‐fold in films printed from amorphous aggregates compared to those from semicrystalline aggregates. This work shows that by tuning the precise structure of solution aggregates, the assembly pathways and the resulting thin‐film morphology and device properties can be drastically tuned.

36 MATERIALS SCIENCE↗

Creating Favorable Pt/Co Interfaces via a Two‐Step Approach for Constructing Highly Durable PtCo Intermetallic Fuel Cell Catalysts

Structurally ordered PtCo intermetallics are one of the most promising oxygen-reduction catalysts in proton exchange membrane fuel cells (PEMFCs) due to their intrinsically improved catalytic activity and stability relative to PtCo solid-solution alloys. However, increasing the heating temperature to achieve a desirable high degree of ordering results in severe particle agglomeration and low mass activity and stability. Herein, a two-step synthesis approach is developed to create an L1 2 -Pt 3 Co intermetallic structure with an increased ordering degree and well-dispersed ultrafine particles. The first step of the synthesis yields ultrafine Pt nanoparticles that are well-dispersed on the ZIF-8-derived carbon support. The second adsorption step enables us to fine-tune the Pt and Co interfaces, assisted by optimal amino acids, to establish a favorable Co-rich environment around fine Pt nanoparticles, facilitating Co diffusion into the Pt crystalline under mild thermal conditions (<800 °C). In conclusion, this two-step ordered L1 2 -Pt 3 Co catalyst is systematically evaluated using membrane electrode assemblies under heavy-duty vehicle (HDV) conditions and demonstrated exceptional performance and durability, retaining 1.35 A cm -2 only a 7% loss in current density at 0.7 V after an extensive accelerated stress test of 150,000 voltage cycles.

30 DIRECT ENERGY CONVERSION↗

Reactive Carbide‐Based Synthesis and Microstructure of NASICON Sodium Metal All Solid‐State Electrolyte

Reactive carbide precursor-based synthesis of NASICON-type NZSP (Na 1+x Zr 2 Si x P 3-x O 12 ) solid-state electrolyte (SSE) is demonstrated, in contrast to the established oxide-based approach. Exothermic decomposition of ZrC and SiC in air homogenizes microstructure, yielding 98% compact density after conventional sintering at 1200 °C. Quantitative stereology demonstrates that significant microstructural differences are present. Compacts of carbide-derived Carb-NZSP are 98% dense with a secondary zirconium oxide (ZrO 2 ) volume fraction of 0.2% ± 0.3%, versus 93% dense and 3% ± 1% for oxide-derived baseline. For Carb-NZSP, the secondary glassy phosphate phase is agglomerated, while for baseline, it is dispersed and percolated. Electrochemical testing combined with post-mortem analysis demonstrates how microstructural control of secondary phases is critical for dendrite suppression: Carb-NZSP critical current density (CCD) is 3.1 ± 0.8 mA cm −2 at 0.1 mAh cm −2 , versus 1.0 ± 0.7 mA cm −2 at 0.1 mAh cm −2 . Cryogenic focused ion beam (cryo-FIB) analysis demonstrates that in both materials, the porous 2D sheet-like sodium metal dendrites propagate around and subsume NZSP grains, likely following a path enriched with glassy phase and with porosity. Dendrites also flow around isolated zirconia particles. Phase field simulation reveals deflection of dendrites by mechanically tough zirconia, while brittle glassy phase accelerates dendrite growth, especially when finely distributed.

36 MATERIALS SCIENCE↗

Constructing Highly Durable Fuel Cell Catalysts Through Integrating Graphitic Shell‐Protected Composite Carbon Support with Gaseous Co Deposition‐Driven PtCo Intermetallics

Metal dissolution, nanoparticle agglomeration, and carbon support corrosion cause significant performance degradation of current PtCo catalysts under acidic and oxidative oxygen reduction reaction. Here, in this study, an integrated strategy is presented to design high-performance Pt 3 Co intermetallic catalysts by regulating gaseous Co deposition-driven diffusion into Pt nanoparticles supported on a composite carbon. The composite carbon is derived from ZIF-8/polyaniline, consisting of a high-surface-area (HSC) core and a protective graphitic shell (GS), which is employed to design 40 wt.% Pt/HSC@GS catalyst. The corresponding membrane electrode assemblies (MEAs) can maintain 1.09 A cm −2 at 0.7 V (20. 7% loss) after 10 000 cycles (1.0–1.5 V for carbon stability) and 1.15 A cm −2 (16.1% loss) after 150 000 cycles (0.60–0.95 V for catalyst stability). A ordered Pt 3 Co intermetallic is synthesized via a gaseous Co-deposition process, which yields a homogeneous Co-rich layer onto the Pt nanoparticles on the composite support, thereby facilitating Co diffusion into Pt crystal during subsequent ordering annealing to form the ordered intermetallic structure. This gaseous deposition leads to a thin carbon layer on PtCo nanoparticles, inhibiting particle growth during the annealing and mitigating Co dissolution under dynamic electrochemical conditions. The PtCo catalyst achieves impressive MEA performance and long-term durability (1.45 A cm −2 at 0.7 V after 120 000 cycles) under heavy-duty conditions.

30 DIRECT ENERGY CONVERSION↗

Ligand‐Induced Crystallization Control in MAPbBr 3 Hybrid Perovskites for High Quality Nanostructured Films

AbstractControlling the formation of hybrid perovskite thin films is crucial in obtaining high‐performance optoelectronic devices, since factors like morphology and film thickness have a profound impact on a film's functionality. For light‐emitting applications grain sizes in the sub‐micrometer‐range have previously shown enhanced brightness. It is therefore crucial to develop simple, yet reliable methods to produce such films. Here, a solution‐based synthesis protocol for the on‐substrate formation of MAPbBr3 (MA = methylammonium) nanostructures by adding the bifunctional rac‐3‐aminobutyric acid to the precursor solution is reported. This synthesis route improves key optical properties such as photoluminescence quantum yields and life times of excited states by inducing a controlled slow‐down of the film formation and suppressing agglomeration effects. In situ spectroscopy reveals a delayed and slowed down crystallization process, which achieves synthesis of perovskite structures with much reduced defect densities. Further, aggregation can be controlled by the amount of amino acid added and adjusting the synthesis protocol allows to produce cubic crystallites with targeted size from nanometer to micrometer scales. The nanocrystalline MAPbBr3 samples show enhanced amplified spontaneous emission (ASE) intensities, reduced ASE thresholds and purer ASE signals, compared to pristine films, even under intense optical driving, making them promising structures for lasing applications.

36 MATERIALS SCIENCE↗

A Sustainable Multi-Dimensional Printable Material

Polymeric materials are usually tailored for specific functionality. A single polymer exhibiting multiple simultaneous functionalities often requires intricate molecular architecture, which is difficult to manufacture at scale because of its complex synthesis routes. In this work, a facile, partly renewable composition—prepared via reactive melt processing—that induces tunable functionalities such as 3D printability, shape recovery, and self-healing while exhibiting satisfactory mechanical properties is reported. The system with a hydrogen-bonded 3D network consists of thermally reversible nano-scale agglomerates of sustainable, rigid phenolic oligomers and crystallizable flexible polymer. Local molecular mobility and temperature-dependent relaxation and recovery of the non-equilibrium networked states enable exploiting these simultaneous functionalities. Transitions involving solidification and structure stabilization at ambient temperature spanning several hours after preheating only at 70 °C directly contrast typical thermoplastic or thermoplastic elastomer behaviors. Results from this study can inform the design of future rheology modifiers and materials for soft robotics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗