Search NASA⌕ Search

SEARCH · Search NASA

Results for “Aggregative growth”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Medium controlled aggregative growth as a key step in mesoporous silica nanoparticle formation

Near monodisperse mesoporous silica nanoparticles (MSN) represent a promising and rapidly developing type of mesoporous silica materials; however, the vast data on their synthesis remains unorganized and ill-understood. We systematically studied the formation of MSN under basic and neutral conditions using various temperatures, CTAB concentrations, hydrolyzing agents (triethanolamine, ammonia, phosphate buffers), and media with different colloidal stabilization properties (with ethanol as a cosolvent and monovalent salts). In the typical conditions for the preparation of stable MSN colloids, the particle size was controlled by colloidal stabilization by the medium (solvent type, ionic strength, and surfactant concentration) in agreement with the “aggregative growth” mechanism, rather than by solely the hydrolysis and condensation rates conventionally used for data interpretation in the classical nucleation theory. Medium properties (pH, ion types and concentration, polarity) also defined the efficiency of silica-surfactant cooperative self-assembly, which directly affected the porosity, mesopore size and pore wall thickness. Interestingly, this traditional silica-surfactant route showed a limited effect on the particle size, emphasizing the dominating role of colloidal stabilization in the studied reaction conditions. In situ pH measurements showed that every reaction medium has unique pH evolution profiles depending on the buffer capacity, hydrolysis and condensation rates. Reaction systems that fail to maintain the working pH can lead to non-porous products or undesired particle morphology and size distribution. The established particle formation mechanism allowed us to formulate comprehensive guidelines for preparing relatively concentrated colloids of near monodisperse (PDI 5–15%) mesoporous 30–700 nm silica spheres with variable porosity and mesopore size. Here, these findings will be particularly useful in designing new mesoporous silica-containing materials for biomedical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Shape Control of Colloidal Semiconductor Nanocrystals through Thermodynamically Driven Aggregative Growth

The optoelectronic properties of colloidal semiconductor nanocrystals (NCs) can be manipulated by changing their geometric shapes. The precise synthetic control over particle morphologies, however, has remained elusive. Conventional growth techniques rely on the kinetic assembly of atomic units, where supersaturation and precipitation processes can lead to a broad distribution of particle shapes. In this paper, we demonstrate that replacing atomic precursors with small-size nanocrystals as building blocks for larger colloids offers an easier, more predictive control over nanoparticle shape evolution. The reported growth strategy is illustrated via shape-selective syntheses of CdSe and CdS NC cubes, spheres, rods, as well as unprecedented “donut” and ring-like structures. Growth of desired particle morphologies was achieved by choosing an appropriate reaction solvent that minimizes the surface free energy through a unique shape formation. This so-called "aggregative growth mechanism" is explained using a thermodynamic model for interacting viscous colloids. We expect that this novel growth strategy will offer a viable platform for shape–selective synthesis of many inorganic colloids, providing pathways to optimizable optoelectronic materials.

36 MATERIALS SCIENCE↗
NASA NTRS1995

The Averaged Face Growth Rates of lysozyme Crystals: The Effect of Temperature

Measurements of the averaged or macroscopic face growth rates of lysozyme crystals are reported here for the (110) face of tetragonal lysozyme, at three sets of pH and salt concentrations, with temperatures over a 4-22 C range for several protein concentrations. The growth rate trends with supersaturation were similar to previous microscopic growth rate measurements. However, it was found that at high super-saturations the growth rates attain a maximum and then start decreasing. No 'dead zone' was observed but the growth rates were found to approach zero asymptotically at very low super-saturations. The growth rate data also displayed a dependence on pH and salt concentration which could not be characterized solely by the super-saturation. A complete mechanism for lysozyme crystal growth, involving the formation of an aggregate growth unit, mass transport of the growth unit to the crystal interface and faceted crystal growth by growth unit addition, is suggested. Such a mechanism may provide a more consistent explanation for the observed growth rate trends than those suggested by other investigators. The nutrient solution interactions leading to the formation of the aggregate growth unit may, thus, be as important as those occurring at the crystal interface and may account for the differences between small molecule and protein crystal growth.

Nadarajah, Arunan↗
NASA NTRS1997

Growth Mechanism of the (110) Face of Tetragonal Lysozyme Crystals

The measured macroscopic growth rates of the (110) face of tetragonal lysozyme show an unexpectedly complex dependence on the supersaturation. In earlier studies it has been shown that an aggregate growth unit could account for experimental growth-rate trends. In particular molecular packing and interactions in the growth of the crystal were favored by completion of the helices along the 4, axes. In this study the molecular orientations of the possible growth units and the molecular growth mechanism were identified. This indicated that growth was a two-step process: aggregate growth units corresponding to the 4, helix are first formed in the bulk solution by stronger intermolecular bonds and then attached to the crystal face by weaker bonds. A more comprehensive analysis of the measured (110) growth rates was also undertaken. They were compared with the predicted growth rates from several dislocation and two-dimensional nucleation growth models, employing tetramer and Octamer growth units in polydisperse solutions and monomer units in monodisperse solutions. The calculations consistently showed that the measured growth rates followed the expected model relations with octamer growth units, in agreement with the predictions from the molecular level analyses.

Nadarajah, Arunan↗
NASA NTRS1990

Growth hormone aggregates in the rat adenohypophysis

Although it has been known for some time that GH aggregates are contained within the rat anterior pituitary gland, the role that they might play in pituitary function is unknown. The present study examines this issue using the technique of Western blotting, which permitted visualization of 11 GH variants with apparent mol wt ranging from 14-88K. Electroelution of the higher mol wt variants from gels followed by their chemical reduction with beta-mercaptoethanol increased GH immunoassayability by about 5-fold. With the blot procedure we found 1) that GH aggregates greater than 44K were associated with a 40,000 x g sedimentable fraction; 2) that GH aggregates were not present in glands from thyroidectomized rats, but were in glands from the thyroidectomized rats injected with T4; 3) that GH aggregates were uniquely associated with a heavily granulated somatotroph subpopulation isolated by density gradient centrifugation; and 4) that high mol wt GH forms were released from the dense somatotrophs in culture, since treatment of the culture medium with beta-mercaptoethanol increased GH immunoassayability by about 5-fold. Taken together, the results show that high mol wt GH aggregates are contained in secretory granules of certain somatotrophs and are also released in aggregate form from these cells in vitro.

NASA Discipline Cell Biology↗
DOE OSTI2021

Bridging the thermodynamics and kinetics of temperature-induced morphology evolution in polymer/fullerene organic solar cell bulk heterojunction

The performance of organic solar cells (OSC) critically depends on the morphology of the active layer. After deposition, the active layer is in a metastable state and prone to changes that lead to cell degradation. Here, a high efficiency fullerene:polymer blend is used as a model system to follow the temperature-induced morphology evolution through a series of thermal annealing treatments. Electron microscopy analysis of the nano-scale phase evolution during the early stages of thermal annealing revealed that spinodal decomposition, i.e. spontaneous phase separation with no nucleation stage, is possibly responsible for the formation of a fine scale bicontinuous structure. In the later evolution stages, large polycrystalline fullerene aggregates are formed. Optical microscopy and scattering revealed that aggregate-growth follows the Johnson–Mehl–Avrami–Kolmogorov equation indicating a heterogeneous transformation process, i.e., through nucleation and growth. These two mechanisms, spinodal decomposition vs. nucleation and growth, are mutually exclusive and their co-existence is surprising. This unexpected observation is resolved by introducing a metastable monotectic phase diagram and showing that the morphology evolution goes through two distinct and consecutive transformation processes where spinodal decomposition of the amorphous donor:acceptor blend is followed by nucleation and growth of crystalline acceptor aggregates. Lastly, this unified thermodynamic and kinetic mechanism allows us to correlate the morphology evolution with OSC degradation during thermal annealing.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Nucleation, Growth, and Aggregation of Todorokite Nanoparticles from Both Geochemical and Materials Science Perspectives (Final Technical Report)

A vast amount of manganese (Mn) nodules exists in ocean sediments, covering about 30% of the ocean floor. Tunneled and layered Mn(IV) oxides, hereafter called TMOs and LMOs, are the primary mineral phases hosting Mn. Owing to their unique structure and properties, these Mn oxides are highly enriched in transition metals, platinum group metals, and rare earth elements, up to several percentages in weight. Thus, many metals are stored in these nodules and the nodules have thus been increasingly considered for their potential as a source of strategic metals for national security applications and the energy industry. The nodules also play an important role in trace metal biogeochemical cycling in the ocean because they control the partition and distribution of trace metals in oceanic sediments. Layered and tunneled structures differ in their mineralogical and chemical properties. For example, TMOs contain fewer metals compared to LMOs in ocean nodules. Therefore, the relative proportion of the two types of minerals in ocean nodules determines the metal sequestration capacities of the nodules, hence the amount of metals stored in the nodules and metal cycling in oceans. The overall objective of this study is to investigate the mechanisms of layered to tunneled structural transform driven by redox reactions. Specifically, we focus on the redox reactions between Mn(IV) and Mn(II) because they often coexist during Mn redox cycling.

58 GEOSCIENCES↗
NASA NTRS1993

Gas-Grain Simulation Facility (GGSF). Volume 1: Stage 1 facility definition studies

The Gas-Grain Simulation Facility (GGSF) is a facility-type payload to be included in the Space Station Freedom (SSF). The GGSF is a multidisciplinary facility that will accommodate several classes of experiments, including exobiology, planetary science, atmospheric science, and astrophysics. The physical mechanisms envisioned to be investigated include crystal growth, aggregation, nucleation, coagulation, condensation, collisions, fractal growth, cycles of freezing and evaporation, scavenging, longevity of bacteria, and more. TRW performed a Phase A study that included analyses of the science and technical (S&T) requirements, the development of facility functional requirements, and a conceptual design of the facility. The work that was performed under Stage 1 of the Phase A study and the results to date are summarized. In this stage, facility definition studies were conducted in sufficient detail to establish the technical feasibility of the candidate strawman experiments. The studies identified technical difficulties, identified required facility subsystems, surveyed existing technology studies and established preliminary facility weight, volume, power consumption, data systems, interface definition, and crew time requirements. The results of this study served as the basis for Stage 2 of the Phase A study in which a conceptual design and a reference design were performed. The results also served as a basis for a related study for a Gas-Grain Simulation Experiment Module (GGSEM), which is an apparatus intended to perform a subset of the GGSF experiments on board a low-Earth-orbiting platform.

Gat, Nahum↗
NASA NTRS1998

Growth of (101) Faces of Tetragonal Lysozyme Crystals: Determination of the Growth Mechanism

Measurements of the macroscopic growth rates of the (101) face of tetragonal lysozyme crystals indicate an unusual dependence on the supersaturation (Forsythe, Nadarajah & Pusey, 1998), similar to that observed for the (110) face. As done before for the (110) face, in this study the surface packing arrangement for the (101) face was constructed, based on earlier microscopic observations and theoretical analysis of the internal molecular packing. This allowed the minimum growth unit for this face to be identified as a tetramer corresponding to a single turn of helices centered about the 4(sub 3) axes, and the minimum growth step to be of unimolecular height. A macroscopic mathematical model for the growth of the (101) face was developed, based on the formation of aggregate growth units in solution and the addition of a unit to the crystal face by dislocation and two-dimensional nucleation mechanisms. The calculations showed that the best fits were obtained for tetramer or octamer growth units in this model, indicating that average size of the growth unit participating in the growth process was between these two sizes.

Li, Meirong↗
DOE OSTI2020

Taxon-specific microbial growth and mortality patterns reveal distinct temporal population responses to rewetting in a California grassland soil

Abstract Microbial activity increases after rewetting dry soil, resulting in a pulse of carbon mineralization and nutrient availability. The biogeochemical responses to wet-up are reasonably well understood and known to be microbially mediated. Yet, the population level dynamics, and the resulting changes in microbial community patterns, are not well understood as ecological phenomena. Here, we used sequencing of 16S rRNA genes coupled with heavy water (H218O) DNA quantitative stable isotope probing to estimate population-specific rates of growth and mortality in response to a simulated wet-up event in a California annual grassland soil. Bacterial growth and mortality responded rapidly to wet-up, within 3 h, and continued throughout the 168 h incubation, with patterns of sequential growth observed at the phylum level. Of the 37 phyla detected in the prewet community, growth was found in 18 phyla while mortality was measured in 26 phyla. Rapid growth and mortality rates were measurable within 3 h of wet-up but had contrasting characteristics; growth at 3 h was dominated by select taxa within the Proteobacteria and Firmicutes, whereas mortality was taxonomically widespread. Furthermore, across the community, mortality exhibited density-independence, consistent with the indiscriminate shock resulting from dry-down and wet-up, whereas growth was density-dependent, consistent with control by competition or predation. Total aggregated growth across the community was highly correlated with total soil CO2 production. Together, these results illustrate how previously “invisible” population responses can translate quantitatively to emergent observations of ecosystem-scale biogeochemistry.

58 GEOSCIENCES↗
NASA NTRS2023

Can the Streaming Instability Form the First Planetesimals in Globally Turbulent Protoplanetary Disks?

Understanding the formation of the first planetesimals remains key to deciphering the history of planet formation within our own solar system and beyond. Evidence from the vast meteorite record [e.g., 1] as well as observations [e.g., 2] strongly suggest that the first planetesimals, and perhaps giant planet core accretion occurred well within the first million years of disk evolution. Moreover, chemical and lithological mixing as well as observations of line-broadening in protoplanetary disks (PPDs) [e.g., 3-6] suggest that the solar system nebula in this epoch was weakly-to-moderately turbulent in the regions where particle growth is of the greatest interest [7-8]. It is a well-known though that global hydrodynamic turbulence complicates particle growth due to a slew of barriers that can slow or even stall particle or aggregate growth at pebble sizes (with corresponding small particle Stokes numbers St) that can lead to loss to the central star via radial drift before planetesimals can ever form [9,10], requiring that some other mechanism come into play that collects growth-frustrated pebbles into gravitationally bound multi-km bodies – objects that are “born big” [11]. The current leading candidate for such a “leap-frog” mechanism is the so-called Streaming Instability (SI), a gas-drag mediated momentum exchange resonance in which the relative velocity between the particle component and a rotating gaseous fluid can lead to high densities in the particle field [12], which has been invoked in a number of recent PPD models that include a turbulent intensity α [e.g., 13-14] as the defacto mechanism for planetesimal formation if conditions for the SI (depending on particle St and the solids-to-gas mass ratio) are satisfied. However, these previous works use conditions established from occurrence studies for the onset of SI in laminar disks [15-17] in which the only source of turbulence is that self-generated by the settling particle layer, and not externally driven global turbulence. Recent analytical theories of the SI subject to global turbulence predict much more stringent conditions for the effectiveness of the SI than the laminar case [18-19]. Thus, whether the efficient operation of the SI can be attained in realistic models of the solar nebula have yet to be established. In this work, we ask whether the conditions under which the SI can produce gravitationally bound particle overdensities can actually be met in the first million years of evolution in globally turbulent PPDs.

P R Estrada↗
NASA NTRS2005

Physical and hydraulic properties of baked ceramic aggregates used for plant growth medium

Baked ceramic aggregates (fritted clay, arcillite) have been used for plant research both on the ground and in microgravity. Optimal control of water and air within the root zone in any gravity environment depends on physical and hydraulic properties of the aggregate, which were evaluated for 0.25-1-mm and 1-2-mm particle size distributions. The maximum bulk densities obtained by any packing technique were 0.68 and 0.64 g cm-3 for 0.25-1-mm and 1-2-mm particles, respectively. Wettable porosity obtained by infiltration with water was approximately 65%, substantially lower than total porosity of approximately 74%. Aggregate of both particle sizes exhibited a bimodal pore size distribution consisting of inter-aggregate macropores and intra-aggregate micropores, with the transition from macro- to microporosity beginning at volumetric water content of approximately 36% to 39%. For inter-aggregate water contents that support optimal plant growth there is 45% change in water content that occurs over a relatively small matric suction range of 0-20 cm H2O for 0.25-1-mm and 0 to -10 cm H2O for 1-2-mm aggregate. Hysteresis is substantial between draining and wetting aggregate, which results in as much as a approximately 10% to 20% difference in volumetric water content for a given matric potential. Hydraulic conductivity was approximately an order of magnitude higher for 1-2-mm than for 0.25-1-mm aggregate until significant drainage of the inter-aggregate pore space occurred. The large change in water content for a relatively small change in matric potential suggests that significant differences in water retention may be observed in microgravity as compared to earth.

NASA Center JSC↗
NASA NTRS1998

Catastrophic Collapse of Particulate Clouds: Implications From Aggregation Experiments in the USML-1 and USML-2 Glovebox

Experiments with electrostatic aggregation of well-dispersed (nominally, mono-dispersed), freely suspended particles in the United States Microgravity Laboratory (USML) Glovebox have determined that filamentary aggregates are a universal product of grain interactions in relatively dense particulate clouds. Aggregate growth from the experimental particle clouds primarily involves dipole-dipole interactions for nonconducting materials; dipole interactions account for both attraction between grains as well as the cohesive force that maintains the integrity of the filamentary structures. When a cloud undergoes a turbulent-to-quiescent transition after damping of fluid and ballistic grain motions, aggregation occurs almost instantaneously and the cloud is transformed into a population of "heavier" clusters of material with organized electrical structures. This abrupt transformation could initiate catastrophic gravitational collapse of certain regions of particulate clouds, thus controlling the longevity and fate of cloud systems as diverse as protoplanetary dust disks and volcanic eruption plumes.

Marshall, John↗
NASA NTRS1989

Collisions of macroscopic fluffy aggregates in the primordial solar nebula and the formation of planetesimals

The characteristics of submicron-size grains lead to the conclusion that, with relative velocities under tens of meters per second deduced for the early stages of accretion in the solar nebula, bodies of meter dimension, were low-density, compressible aggregates. The collision mechanism appropriate to such objects is explored here. The results of representative collisions are summarized which show that the penetration is only a fraction of the radius of the impacting body. Hence, all but near-grazing collisions lead to merger of the two bodies. Aggregate growth occurs without substantially increasing the mean density, but small region with densities about 60 percent of the bulk density will occur in a collision.

Donn, B.↗
NASA NTRS1992

Fractals and cosmological large-scale structure

Observations of galaxy-galaxy and cluster-cluster correlations as well as other large-scale structure can be fit with a 'limited' fractal with dimension D of about 1.2. This is not a 'pure' fractal out to the horizon: the distribution shifts from power law to random behavior at some large scale. If the observed patterns and structures are formed through an aggregation growth process, the fractal dimension D can serve as an interesting constraint on the properties of the stochastic motion responsible for limiting the fractal structure. In particular, it is found that the observed fractal should have grown from two-dimensional sheetlike objects such as pancakes, domain walls, or string wakes. This result is generic and does not depend on the details of the growth process.

Luo, Xiaochun↗
NASA NTRS2008

Use of Potassium Citrate to Reduce the Risk of Renal Stone Formation During Spaceflight

Introduction: NASA s Vision for Space Exploration centers on exploration class missions including the goals of returning to the moon and landing on Mars. One of NASA s objectives is to focus research on astronaut health and the development of countermeasures that will protect crewmembers during long duration voyages. Exposure to microgravity affects human physiology and results in changes in the urinary chemical composition favoring urinary supersaturation and an increased risk of stone formation. Nephrolithiasis is a multifactorial disease and development of a renal stone is significantly influenced by both dietary and environmental factors. Previous results from long duration Mir and short duration Shuttle missions have shown decreased urine volume, pH, and citrate levels and increased calcium. Citrate, an important inhibitor of calcium-containing stones, binds with urinary calcium reducing the amount of calcium available to form stones. Citrate inhibits renal stone recurrence by preventing crystal growth, aggregation, and nucleation and is one of the most common therapeutic agents used to prevent stone formation. Methods: Thirty long duration crewmembers (29 male, 1 female) participated in this study. 24-hour urines were collected and dietary monitoring was performed pre, in, and postflight. Crewmembers in the treatment group received two potassium citrate (KCIT) pills, 10 mEq/pill, ingested daily beginning 3 days before launch, all inflight days and through 14 days postflight. Urinary biochemical and dietary analyses were completed. Results: KCIT treated subjects exhibited decreased urinary calcium excretion and maintained the levels of calcium oxalate supersaturation risk at their preflight levels. The increased urinary pH levels in these subjects reduced the risk of uric acid stones. Discussion: The current study investigated the use of potassium citrate as a countermeasure to minimize the risk of stone formation during ISS missions. Results suggest that supplementation with potassium citrate decreases the risk of stone formation during and immediately after spaceflight.

Whitson, P. A.↗
NASA NTRS2009

Renal Stone Risk during Spaceflight: Assessment and Countermeasure Validation

NASA's Vision for Space Exploration centers on exploration class missions including the goals of returning to the moon and landing on Mars. One of NASA's objectives is to focus research on astronaut health and the development of countermeasures that will protect crewmembers during long duration voyages. Exposure to microgravity affects human physiology and results in changes in the urinary chemical composition favoring urinary supersaturation and an increased risk of stone formation. Nephrolithiasis is a multifactorial disease and development of a renal stone is significantly influenced by both dietary and environmental factors. Previous results from long duration Mir and short duration Shuttle missions have shown decreased urine volume, pH, and citrate levels and increased calcium. Citrate, an important inhibitor of calcium-containing stones, binds with urinary calcium reducing the amount of calcium available to form stones. Citrate inhibits renal stone recurrence by preventing crystal growth, aggregation, and nucleation and is one of the most common therapeutic agents used to prevent stone formation. Methods: Thirty long duration crewmembers (29 male, 1 female) participated in this study. 24-hour urines were collected and dietary monitoring was performed pre-, in-, and postflight. Crewmembers in the treatment group received two potassium citrate (KCIT) pills, 10 mEq/pill, ingested daily beginning 3 days before launch, all in-flight days and through 14 days postflight. Urinary biochemical and dietary analyses were completed. Results: KCIT treated subjects exhibited decreased urinary calcium excretion and maintained the levels of calcium oxalate supersaturation risk at their preflight levels. The increased urinary pH levels in these subjects reduced the risk of uric acid stones. Discussion: The current study investigated the use of potassium citrate as a countermeasure to minimize the risk of stone formation during ISS missions. Results suggest that supplementation with potassium citrate decreases the risk of stone formation during and immediately after spaceflight.

Whitson, Peggy A.↗
NASA NTRS1996

Analysis of Monomer Aggregation and Crystal Growth Rates of Lysozyme

This project was originally conceived to analyze the extensive data of tetragonal lysozyme crystal growth rates collected at NASA/MSFC by Dr. Marc L. Pusey's research group. At that time the lack of analysis of the growth rates was hindering progress in understanding the growth mechanism of tetragonal lysozyme and other protein crystals. After the project was initiated our initial analysis revealed unexpected complexities in the growth rate behavior. This resulted in an expansion in the scope of the project to include a comprehensive investigation of the growth mechanisms of tetragonal lysozyme crystals. A discussion of this research is included as well a list of presentations and publications resulting from the research. This project contributed significantly toward the education of several students and fostered extensive collaborations between investigators.

Nadarajah, Arunan↗