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At least 235 records · Page 13

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NASA NTRS2000

Size Exclusion Chromatography Studies of the Initial Self-Association Steps of Chicken Egg White Lysozyme Nucleation

Nucleation is one of the least understood aspects of crystallogenesis. In the case of macromolecule nucleation, this understanding is further hampered by uncertainty over what precisely is being discussed. We define the process of solute self-association (aggregation, oligomerization, interaction, clustering, etc.) whereby n-mers (n > or = 2) having a crystallographic or nascent crystallographic arrangement leading to the critical nucleus reversibly form in the solution, to be part of the nucleation process. This reversible self-association process is a fundamental part of the nucleation process, and occurs as a function of the solute concentration. In the case of chicken egg white lysozyme, a considerable body of experimental evidence leads us to the conclusion that it also forms the crystal growth units. Size exclusion chromatography is a simple and direct method for determining the equilibrium constants for the self-association process. A Pharmacia FPLC system was used to provide accurate solution flow rates. The column, injection valve, and sample loop were all mounted within a temperature-controlled chamber. Chromatographically re-purified lysozyme was first dialyzed against the column equilibration buffer, with injection onto the column after several hours pre-incubation at the running temperature. Preliminary experiments, were carried out using a Toyopearl HW-50F column (1 x 50cm), equilibrated with 0.1 M sodium acetate, 5% sodium chloride, pH 4.6, at 15C. Protein concentrations from 0.1 to 4 mg/ml were employed (C(sub sat) = 1.2 mg/ml). The data from several different protein preparations consistently shows a progressively decreasing elution volume with increasing protein concentration, indicating that reversible self-association is occurring. The dotted line indicates the monomeric lysozyme elution volume. However, lysozyme interacts with the column matrix in these experiments, which complicates data analysis.Accordingly, we are testing silica-based HPLC columns in an effort to eliminate this problem and substantially reduce the column volume and experimental run time. The results and data analysis from these and subsequent experiments will be presented.

Ewing, Felecia↗

NASA NTRS2000

Zinc Nucleation and Growth in Microgravity

We report our experiences with zinc nucleation in a microgravity environment aboard NASA's Reduced Gravity Research Facility. Zinc vapor is produced by a heater in a vacuum chamber containing argon gas. Nucleation is induced by cooling and its onset is easily detected visually by the appearance of a cloud of solid, at least partially crystalline zinc particles. Size distribution of these particles is monitored in situ by photon correlation spectroscopy. Samples of particles are also extracted for later analysis by SEM. The initially rapid increase in particle size is followed by a slower period of growth. We apply Scaled Nucleation Theory to our data and find that the derived critical temperature of zinc, the critical cluster size at nucleation, and the surface tension values are all in reasonably good agreement with their accepted literature values.

Michael, B. Patrick↗

NASA NTRS2001

Ice Nucleation in Deep Convection

The processes controlling production of ice crystals in deep, rapidly ascending convective columns are poorly understood due to the difficulties involved with either modeling or in situ sampling of these violent clouds. A large number of ice crystals are no doubt generated when droplets freeze at about -40 C. However, at higher levels, these crystals are likely depleted due to precipitation and detrainment. As the ice surface area decreases, the relative humidity can increase well above ice saturation, resulting in bursts of ice nucleation. We will present simulations of these processes using a large-eddy simulation model with detailed microphysics. Size bins are included for aerosols, liquid droplets, ice crystals, and mixed-phase (ice/liquid) hydrometers. Microphysical processes simulated include droplet activation, freezing, melting, homogeneous freezing of sulfate aerosols, and heterogeneous ice nucleation. We are focusing on the importance of ice nucleation events in the upper part of the cloud at temperatures below -40 C. We will show that the ultimate evolution of the cloud in this region (and the anvil produced by the convection) is sensitive to these ice nucleation events, and hence to the composition of upper tropospheric aerosols that get entrained into the convective column.

Jensen, Eric↗

NASA NTRS1995

A New Theory of Nucleate Pool Boiling in Arbitrary Gravity

Heat transfer rates specific to nucleate pool boiling under various conditions are determined by the dynamics of vapour bubbles that are originated and grow at nucleation sites of a superheated surface. A new dynamic theory of these bubbles has been recently developed on the basis of the thermodynamics of irreversible processes. In contrast to other existing models based on empirically postulated equations for bubble growth and motion, this theory does not contain unwarrantable assumptions, and both the equations are rigorously derived within the framework of a unified approach. The conclusions of the theory are drastically different from those of the conventional models. The bubbles are shown to detach themselves under combined action of buoyancy and a surface tension force that is proven to add to buoyancy in bubble detachment, but not the other way round as is commonly presumed. The theory ensures a sound understanding of a number of so far unexplained phenomena, such as effect caused by gravity level and surface tension on the bubble growth rate and dependence of the bubble characteristics at detachment on the liquid thermophysical parameters and relevant temperature differences. The theoretical predictions are shown to be in a satisfactory qualitative and quantitative agreement with observations. When being applied to heat transfer at nucleate pool boiling, this bubble dynamic theory offers an opportunity to considerably improve the main formulae that are generally used to correlate experimental findings and to design boiling heat removal in various industrial applications. Moreover, the theory makes possible to pose and study a great deal of new problems of essential impact in practice. Two such problems are considered in detail. One problem concerns the development of a principally novel physical model for the first crisis of boiling. This model allows for evaluating critical boiling heat fluxes under various conditions, and in particular at different gravity levels, with a good agreement with experimental evidence. The other problem bears upon equilibrium shapes of a detached bubble near a heated surface in exceedingly low gravity. In low gravity or in weightlessness, the bubble can remain in the close vicinity of the surface for a long time, and its shape is greatly affected by the Marangoni effect due to both temperature and possible surfactant concentration being nonuniform along the interface. The bubble performs at these conditions like a heat pipe, with evaporation at the bubble lower boundary and condensation at its upper boundary, and ultimately ensures a substantial increase in heat removal as compared with that in normal gravity. Some other problems relevant to nucleate pool and forced convection boiling heat transfer are also discussed.

Buyevich, Y. A.↗

NASA NTRS2002

A Proposed Pathway for the Nucleation and Crystal Growth of the Tetragonal Form of Lysozyme

A number of factors, the shape and charge distribution anisotropy, multiple components in the solution (buffer + counter ion, precipitant, protein, and water), conformational flexibility, and large numbers of intermolecular contacts, all serve as complicating variables in understanding the nucleation and growth mechanism for macromolecules. Intermolecular contacts include hydrogen bonds, van der Waals, hydrophobic, salt bridges, and ion-mediated contacts. The latter interactions are stronger and give specificity while the others are weaker, more prevalent, and more promiscuous, i.e., can lead to a range of possible molecular interactions. We propose that for tetragonal lysozyme, and by extension many other monomeric proteins, there is a solution-phase assembly process to form 4(sub 3) helix structures that are the basic unit for nucleation. The formation of these structures is continuous and concentration dependent. They subsequently also servc as growth units, with that process then being a recapitulation of the nucleation process. The advantages of solution phase assembly are the immediate burying of the strongest interactions, removing them from subsequent participation in the nucleation and growth process, and the introduction of symmetry into the system, which also assists in the assembly process.

Pusey, Marc L.↗

NASA NTRS2002

Triggered Nucleation in Ni60Nb40 Using an Electrostatic Levitator

External triggering of nucleation in an undercooled liquid metal has been performed for the first time in an electrostatically levitated sample of undercooled eutectic Ni60Nb40. With the Electrostatic Levitator (ESL) facility at NASA/MSFC, NiNb alloys were externally nucleated at various undercooling increments. Observation of the resulting microstructure indicates that only one nucleation site is initiated with a trigger if the undercooling is sufficiently high. Well-defined transition zones exist in all the samples. An "anomalous" fine structured eutectic is initially grown from the nucleation point into the undercooled liquid followed by an unexpected variable width transition zone leading to a coarse structured region of dendrites. Our study tends to corroborate the findings of other studies on highly undercooled eutectics regarding a coupled growth zone within which the lamellar structure is formed and outside of which the anomalous is found.

Rathz, T.↗

NASA NTRS2002

Tetragonal Lysozyme Nucleation and Crystal Growth: The Role of the Solution Phase

Lysozyme, and most particularly the tetragonal form of the protein, has become the default standard protein for use in macromolecule crystal nucleation and growth studies. There is a substantial body of experimental evidence, from this and other laboratories, that strongly suggests this proteins crystal nucleation and growth is by addition of associated species that are preformed by standard reversible concentration-driven self association processes in the bulk solution. The evidence includes high resolution AFM studies of the surface packing and of growth unit size at incorporation, fluorescence resonance energy transfer measurements of intermolecular distances in dilute solution, dialysis kinetics, and modeling of the growth rate data. We have developed a selfassociation model for the proteins crystal nucleation and growth. The model accounts for the obtained crystal symmetry, explains the observed surface structures, and shows the importance of the symmetry obtained by self-association in solution to the process as a whole. Further, it indicates that nucleation and crystal growth are not distinct mechanistically, but identical, with the primary difference being the probability that the particle will continue to grow or dissolve. This model also offers a possible mechanism for fluid flow effects on the growth process and how microgravity may affect it. While a single lysozyme molecule is relatively small (M.W. = 14,400), a structured octamer in the 4(sub 3) helix configuration (the proposed average sized growth unit) would have a M.W. = 115,000 and dimensions of 5.6 x 5.6 x 7.6 nm. Direct AFM measurements of growth unit incorporation indicate that units as wide as 11.2 nm and as long as 11.4 nm commonly attach to the crystal. These measurements were made at approximately saturation conditions, and they reflect the sizes of species that both added or desorbed from the crystal surface. The larger and less isotropic the associated species the more likely that it will be oriented to some degree in a flowing boundary layer, even at the low flow velocities measured about macromolecule crystals. Flow-driven effects resulting in misorientation upon addition to and incorporation into the crystal need only be a small fraction of a percentage to significantly affect the resulting crystal. One Earth, concentration gradient driven flow will maintain a high interfacial concentration, i.e., a high level (essentially that of the bulk solution) of solute association at the interface and higher growth rate. Higher growth rates mean an increased probability that misaligned growth units are trapped by subsequent growth layers before they can be desorbed and try again, or that the desorbing species will be smaller than the adsorbing species. In microgravity the extended diffusive boundary layer will lower the interfacial concentration. This results in a net dissociation of aggregated species that diffuse in from the bulk solution, i.e., smaller associated species, which are more likely able to make multiple attempts to correctly bind, yielding higher quality crystals.

Pusey, Marc L.↗

NASA NTRS2003

Kinetics of Nucleation and Crystal Growth in Glass Forming Melts in Microgravity

This flight definition project has the specific objective of investigating the kinetics of nucleation and crystal growth in high temperature inorganic oxide, glass forming melts in microgravity. It is related to one1 of our previous NASA projects that was concerned with glass formation for high temperature containerless melts in microgravity. The previous work culminated in two experiments which were conducted aboard the space shuttle in 1983 and 1985 and which consisted of melting (at 1500 C) and cooling levitated 6 to 8 mm diameter spherical samples in a Single Axis Acoustic Levitator (SAAL) furnace. Compared to other types of materials, there have been relatively few experiments, 6 to 8, conducted on inorganic glasses in space. These experiments have been concerned with mass transport (alkali diffusion), containerless melting, critical cooling rate for glass formation, chemical homogeneity, fiber pulling, and crystallization of glass forming melts. One of the most important and consistent findings in all of these experiments has been that the glasses prepared in microgravity are more resistant to crystallization (better glass former) and more chemically homogeneous than equivalent glasses made on earth (1g). The chemical composition of the melt appears relatively unimportant since the same general results have been reported for oxide, fluoride and chalcogenide melts. These results for space-processed glasses have important implications, since glasses with a higher resistance to crystallization or higher chemical homogeneity than those attainable on earth can significantly advance applications in areas such as fiber optics communications, high power laser glasses, and other photonic devices where glasses are the key functional materials. The classical theories for nucleation and crystal growth for a glass or melt do not contain any parameter that is directly dependent upon the g-value, so it is not readily apparent why glasses prepared in microgravity should be more resistant to crystallization than equivalent glasses prepared on earth. Similarly, the gravity-driven convection in a fluid melt is believed to be the primary force field that is responsible for melt homogenization on earth. Thus, it is not obvious why a glass prepared in space, where gravity-driven convection is ideally absent, would be more chemically homogeneous than a glass identically prepared on earth. The primary objective of the present research is to obtain experimental data for the nucleation rate and crystal growth rate for a well characterized silicate melt (lithium disilicate) processed entirely in space (low gravity) and compare these rates with the nucleation and crystal growth rates for a similar glass prepared identically on earth (1g).

Day, Delbert E.↗

NASA NTRS2003

Studies of Nucleation and Growth, Specific Heat and Viscosity of Undercooled Melts of Quasicrystal and Polytetrahedral-Phase Forming Alloys

From extensive ground based work on the phase diagram and undercooling studies of Ti-Zr-Ni alloys, have clearly identified the composition of three different phases with progressively increasing polytetrahedral order such as, (Ti/Zr), the C14 Laves phase, and the i-phase, that nucleate directly from the undercooled liquid. The reduced undercooling decreases progressively with increasing polytetrahedral order in the solid, supporting Frank s hypothesis. A new facility for direct measurements of the structures and phase transitions in undercooled liquids (BESL) was developed and has provided direct proof of the primary nucleation of a metastable icosahedral phase in some Ti-Zr-Ni alloys. The first measurements of specific heat and viscosity in the undercooled liquid of this alloy system have been completed. Other than the importance of thermo-physical properties for modeling nucleation and growth processes in these materials, these studies have also revealed some interesting new results (such as a maximum of C(sup q, sub p) in the undercooled state). These ground-based results have clearly established the necessary background and the need for conducting benchmark nucleation experiments at the ISS on this alloy system.

Kelton, K. F.↗

NASA NTRS2004

Verification of an Analytical Method for Measuring Crystal Nucleation Rates in Glasses from DTA Data

A recently proposed analytical (DTA) method for estimating the nucleation rates in glasses has been evaluated by comparing experimental data with numerically computed nucleation rates for a model lithium disilicate glass. The time and temperature dependent nucleation rates were predicted using the model and compared with those values from an analysis of numerically calculated DTA curves. The validity of the numerical approach was demonstrated earlier by a comparison with experimental data. The excellent agreement between the nucleation rates from the model calculations and fiom the computer generated DTA data demonstrates the validity of the proposed analytical DTA method.

Ranasinghe, K. S.↗

NASA NTRS2005

Anvil Glaciation in a Deep Cumulus Updraught over Florida Simulated with the Explicit Microphysics Model. I: Impact of Various Nucleation Processes

Simulations of a cumulonimbus cloud observed in the Cirrus regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment (CRYSTAL-FACE) with an advanced version of the Explicit Microphysics Model (EMM) are presented. The EMM has size-resolved aerosols and predicts the time evolution of sizes, bulk densities and axial ratios of ice particles. Observations by multiple aircraft in the troposphere provide inputs to the model, including observations of the ice nuclei and of the entire size distribution of condensation nuclei. Homogeneous droplet freezing is found to be the source of almost all of the ice crystals in the anvil updraught of this particular model cloud. Most of the simulated droplets that freeze to form anvil crystals appear to be nucleated by activation of aerosols far above cloud base in the interior of the cloud ("secondary" or "in cloud" droplet nucleation). This is partly because primary droplets formed at cloud base are invariably depleted by accretion before they can reach the anvil base in the updraught, which promotes an increase with height of the average supersaturation in the updraught aloft. More than half of these aerosols, activated far above cloud base, are entrained into the updraught of this model cloud from the lateral environment above about 5 km above mean sea level. This confirms the importance of remote sources of atmospheric aerosol for anvil glaciation. Other nucleation processes impinge indirectly upon the anvil glaciation by modifying the concentration of supercooled droplets in the upper levels of the mixed-phase region. For instance, the warm-rain process produces a massive indirect impact on the anvil crystal concentration, because it determines the mass of precipitation forming in the updraught. It competes with homogeneous freezing as a sink for cloud droplets. The effects from turbulent enhancement of the warm-rain process and from the nucleation processes on the anvil ice properties are assessed.

Phillips, Vaughan T. J.↗

NASA NTRS2013

Heterogeneous Formation of Polar Stratospheric Clouds- Part 1: Nucleation of Nitric Acid Trihydrate (NAT)

Satellite-based observations during the Arctic winter of 2009/2010 provide firm evidence that, in contrast to the current understanding, the nucleation of nitric acid trihydrate (NAT) in the polar stratosphere does not only occur on preexisting ice particles. In order to explain the NAT clouds observed over the Arctic in mid-December 2009, a heterogeneous nucleation mechanism is required, occurring via immersion freezing on the surface of solid particles, likely of meteoritic origin. For the first time, a detailed microphysical modelling of this NAT formation pathway has been carried out. Heterogeneous NAT formation was calculated along more than sixty thousand trajectories, ending at Cloud Aerosol Lidar with Orthogonal Polarization (CALIOP) observation points. Comparing the optical properties of the modelled NAT with these observations enabled a thorough validation of a newly developed NAT nucleation parameterisation, which has been built into the Zurich Optical and Microphysical box Model (ZOMM). The parameterisation is based on active site theory, is simple to implement in models and provides substantial advantages over previous approaches which involved a constant rate of NAT nucleation in a given volume of air. It is shown that the new method is capable of reproducing observed polar stratospheric clouds (PSCs) very well, despite the varied conditions experienced by air parcels travelling along the different trajectories. In a companion paper, ZOMM is applied to a later period of the winter, when ice PSCs are also present, and it is shown that the observed PSCs are also represented extremely well under these conditions.

Hoyle, C. R.↗

NASA NTRS2017

Ice Nucleation in the Tropical Tropopause Layer: Implications for Cirrus Occurrence, Cirrus Microphysical Properties, and Dehydration of Air Entering the Stratosphere

Recent laboratory experiments have advanced our understanding of the physical properties and ice nucleating abilities of aerosol particles atlow temperatures. In particular, aerosols containing organics will transition to a glassy state at low temperatures, and these glassy aerosols are moderately effective as ice nuclei. These results have implications for ice nucleation in the cold Tropical Tropopause Layer (TTL; 13-19 km). We have developed a detailed cloud microphysical model that includes heterogeneous nucleation on a variety of aerosol types and homogeneous freezing of aqueous aerosols. This model has been incorporated into one-dimensional simulations of cirrus and water vapor driven by meteorological analysis temperature and wind fields. The model includes scavenging of ice nuclei by sedimenting ice crystals. The model is evaluated by comparing the simulated cloud properties and water vapor concentrations with aircraft and satellite measurements. In this presentation, I will discuss the relative importance of homogeneous and heterogeneous ice nucleation, the impact of ice nuclei scavenging as air slowly ascends through the TTL, and the implications for the final dehydration of air parcels crossing the tropical cold-point tropopause and entering the tropical stratosphere.

tropopause↗

DOE OSTI2023

Nucleation dependence of atomic layer deposition on diamond surface termination

Surface termination and interfacial interactions are critical for advanced solid-state quantum applications. Here, in this paper, we demonstrate that atomic layer deposition (ALD) can both provide valuable insight on the chemical environment of the surface, having sufficient sensitivity to distinguish between the common diamond (001) surface termination types and passivate these interfaces as desired. We selected diamond substrates exhibiting both smooth and anomalously rough surfaces to probe the effect of morphology on ALD nucleation. We use high resolution in situ spectroscopic ellipsometry to monitor the surface reaction with sub-angstrom resolution, to evaluate the nucleation of an ALD Al 2 O 3 process as a function of different ex and in situ treatments to the diamond surface. In situ water dosing and high vacuum annealing provided the most favorable environment for nucleation of dimethylaluminum isopropoxide and water ALD. Hydrogen termination passivated both smooth and rough surfaces while triacid cleaning passivated the smooth surface only, with striking effectiveness.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Effect of Sn microalloying on the nucleation of L1 2 Al 3 Zr precipitates in a dilute aluminum-zirconium alloy

While L1 2 -Al 3 Zr nanoprecipitates provide a balance between strengthening and good electrical conductivity, the precipitation of L1 2 -Al 3 Zr in aluminum requires aggressive heat treatments. An improved age-hardening response was observed during isochronal aging of an Al-0.24Zr (wt%) alloy when microalloyed with Sn. A new mechanism termed Low melting point Element-Assisted Nucleation (LEAN) is proposed to explain the lower temperature nucleation of L1 2 -Al 3 Zr precipitates observed in this alloy based on the addition of a low melting point element, such as Sn. Characterization verified the first-principles density functional theory prediction that Zr and Sn atoms cluster during homogenization owing to the favorable binding energy of Zr-Sn-vacancy triplets. Direct microstructural observations revealed these clusters form Sn nanoprecipitates that assist the nucleation of L1 2 -Al 3 Zr at 200°C, where L1 2 -Al 3 Zr precipitation is not expected due to the low diffusivity of Zr atoms in Al. At higher temperatures (≳350°C), the acceleration of L1 2 -Al 3 Zr precipitation is driven by faster Zr diffusion in Al with Sn microalloying and the nuclei formed via the LEAN mechanism. In conclusion, this combination of mechanisms explains the improvement in age hardening through L1 2 -Al 3 Zr precipitation with Sn microalloying.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Direct observation of key aluminum hydroxide prenucleation oligomers for gibbsite nucleation and crystallization in sodium aluminate solution by liquid ToF-SIMS

The mechanism of gibbsite (aluminum hydroxide) crystallization from highly alkaline solutions such as Bayer liquors remains poorly understood, where aluminum (Al) transforms from largely tetrahedrally coordinated aluminate monomers in sodium aluminate solutions into a network of octahedra in gibbsite crystals. A variety of traditional analytical approaches applied to this system do not readily reveal the presence of higher-order oligomeric intermediates. To overcome this limitation, we employed in-situ liquid Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) to examine the Al species present in concentrated sodium aluminate solutions favoring crystallization of gibbsite or sodium aluminate. A complex mixture of Al oligomers was found. By comparing the change in the relative concentration of Al oligomers with +1 and -1 charge, we were able to identify three major Al oligomer candidates, iso-tetramers, iso-pentamers, and cyclic-hexamers, for the nucleation and crystallization of gibbsite. The concentrations of iso-tetramers and iso-pentamers significantly surpass those of cyclic-hexamers. Time-dependent in-situ Raman spectroscopy analysis indicated that the appearance of gibbsite coincided with the peak concentration of these oligomers. The Density-functional theory (DFT) calculation suggests that the formation of iso-oligomers is more favorable than that of cyclic-hexamers. The combined results suggest that iso-tetramers and iso-pentamers play the most substantial role in the nucleation and growth of gibbsite in the sodium aluminate solutions. Our findings also suggest that the oligomers that promote gibbsite crystallization are more stable in dilute sodium aluminate solutions, making these solutions particularly suitable for efficient gibbsite crystallization. In conclusion, our study fills a major knowledge gap in understanding Al speciation that leads to the nucleation and crystallization of gibbsite in concentrated sodium aluminate solutions.

Bayer liquor↗

DOE OSTI2020

Nucleation and growth of α phase in a metastable β-Titanium Ti-5Al-5Mo-5V-3Cr alloy: Influence from the nano-scale, ordered-orthorhombic O" phase and α compositional evolution

We investigated the nucleation and growth of α precipitates in the presence of nano-scale, titanium-rich, ordered-orthorhombic O" precipitates formed during heating at 5 °C/min to 400 °C in a metastable β-Ti alloy, Ti-5Al-5Mo-5V-3Cr. The O" precipitates are found to assist α nucleation by serving as preferential nucleation sites. In the very initial stages of its precipitation, the α phase is found to have formed via a coupled diffusional-displacive mode as titanium-rich plates. At this stage, aluminum partitions equally between the β matrix and the growing α precipitates, but slowly diffuses up-hill into the α phase during isothermal aging at 400 °C for 15 h. The interplay between such pre-formed metastable phases and α can be exploited to tailor the microstructure, by refining the α distribution, and consequently improve the mechanical properties of β-Ti alloys. Finally, our work paves the way for exploiting this cascade of metastable phases for further microstructural engineering of β-Ti alloys.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Indium–Poly(carboxylic acid) Ligand Interactions Modify InP Quantum Dot Nucleation and Growth

Size control through precursor reactivity in InP quantum dot (QD) synthesis has been difficult due to the presence of kinetically persistent InP clusters when using conventional indium carboxylate and tris(trimethylsilyl)phosphine chemistry. However, the advent of indium halide/aminophosphine-based synthesis creates new opportunities to harness precursor design to impact nucleation and growth. Driven to further explore indium coordination as a synthetic handle in InP QD synthesis, we examined the effect of a strongly chelating anion on the nucleation and growth of InP QDs. Increasing the equivalents of metal-chelating aminopoly(carboxylic acid) EDTA ([CH 2 N(CH 2 CO 2 H) 2 ] 2 ) (0–0.75 equiv per indium) is found to decrease the final diameter of InP QDs from 4.5 to 2.3 nm by lowering the initial InP growth rate. This size trend is rationalized by invoking a continuous nucleation model. Control experiments carried out with substoichiometric equivalents of indium do not exhibit a drastic size decrease, pointing to complex effects of EDTA on the indium precursor reactivity. By 1 H NMR spectroscopy, EDTA is identified to form an octahedral complex with indium that is less reactive. Furthermore, this competitive decrease in reactivity and in the effective concentration of indium precursor is proposed to suppress the initial InP growth rates and consequently decrease the final size of the nanocrystals.

36 MATERIALS SCIENCE↗