Surface Kinetics and Stability of Faceted Crystal Growth
The applicability of Gibbs-Thompson Law and other fundamental rules to faceted crystal growth will be discussed. Tutorial lecture will include fundamentals of interface kinetics.
Engineering topics
Publications and source records attributed to Curreri, Peter A..
The applicability of Gibbs-Thompson Law and other fundamental rules to faceted crystal growth will be discussed. Tutorial lecture will include fundamentals of interface kinetics.
The effect of the chemical state of the surface of nanoparticles on the relaxation in the near-surface layer was examined using the concept of the apparent lattice parameter (alp) determined for different diffraction vectors Q. The apparent lattice parameter is a lattice parameter determined either from an individual Bragg reflection, or from a selected region of the diffraction pattern. At low diffraction vectors the Bragg peak positions are affected mainly by the structure of the near-surface layer, while at high Q-values only the interior of the nano-grain contributes to the diffraction pattern. Following the measurements on raw (as prepared) powders we investigated powders cleaned by annealing at 400C under vacuum, and the same powders wetted with water. Theoretical alp-Q plots showed that the structure of the surface layer depends on the sample treatment. Semi-quantitative analysis based on the comparison of the experimental and theoretical alp-Q plots was performed. Theoretical alp-Q relations were obtained from the diffraction patterns calculated for models of nanocrystals with a strained surface layer using the Debye functions.
Macromolecular crystallization is a complex process, involving a system that typically has 5 or more components (macromolecule, water, buffer + counter ion, and precipitant). Whereas small molecules have only a few contacts in the crystal lattice, macromolecules generally have 10's or even 100's of contacts between molecules. These can range from hydrogen bonds (direct or water-mediated), through van der Waals, hydrophobic, salt bridges, and ion-mediated contacts. The latter interactions are stronger and require some specificity in the molecular alignment, while the others are weaker, more prevalent, and more promiscuous, i.e., can be readily broken and reformed between other sites. Formation of a consistent, ordered, 3D structure may be difficult or impossible in the absence of any or presence of too many strong interactions. Further complicating the process is the inherent structural asymmetry of monomeric (single chain) macromolecules. The process of crystal nucleation and growth involves the ordered assembly of growth units into a defined 3D lattice. We suggest that for many macromolecules, particularly those that are monomeric, this involves a preliminary solution-phase assembly process into a growth unit having some symmetry prior to addition to the lattice, recapitulating the initial stages of the nucleation process. If this model is correct then fluids and crystal growth models assuming a strictly monodisperse nutrient solution need to be revised. This model has been developed from experimental evidence based upon face growth rate, AFM, and fluorescence energy transfer data for the nucleation and growth of tetragonal lysozyme crystals.
The Quench Module Insert (QMI) materials processing furnace is being designed to operate for 8000 hours over four years on the International Space Station (ISS) as part of the first Materials Science Research Rack (MSRR-1) of the Materials Science Research Facility (MSRF). The Bridgman-type furnace is being built for the directional solidification processing of metals and alloys in the microgravity environment of space. Most notably it will be used for processing aluminum and related alloys. Designing for the space station environment presents intriguing design challenges in the form of a ten-year life requirement coupled with both limited opportunities for maintenance and resource constraints in the form of limited power and space. The long life requirement has driven the design of several features in the furnace, including the design of the heater core, the selection and placement of the thermocouples, overall performance monitoring, and the design of the chill block. The power and space limitations have been addressed through a compact furnace design using efficient vacuum insulation. Details on these design features, as well as development test performance results to date, are presented.
Experimental evidence indicates a dominant role of solution phase interactions in nucleating and growing tetragonal lysozyme crystals. These interactions are extensive, even at saturation, and may be a primary cause of misoriented regions in crystals grown on Earth. Microgravity, by limiting interfacial concentrations to diffusion-controlled levels, may benefit crystal quality by also reducing the extent of associated species present at the interface.
Microporous materials are framework structures with well-defined porosity, often of molecular dimensions. Zeolites contain aluminum and silicon atoms in their framework and are the most extensively studied amongst all microporous materials. Framework structures with P, Ga, Fe, Co, Zn, B, Ti and a host of other elements have also been made. Typical synthesis of microporous materials involve mixing the framework elements (or compounds, thereof) in a basic solution, followed by aging in some cases and then heating at elevated temperatures. This process is termed hydrothermal synthesis, and involves complex chemical and physical changes. Because of a limited understanding of this process, most synthesis advancements happen by a trial and error approach. There is considerable interest in understanding the synthesis process at a molecular level with the expectation that eventually new framework structures will be built by design. The basic issues in the microporous materials crystallization process include: (1) Nature of the molecular units responsible for the crystal nuclei formation; (2) Nature of the nuclei and nucleation process; (3) Growth process of the nuclei into crystal; (4) Morphological control and size of the resulting crystal; (5) Surface structure of the resulting crystals; (6) Transformation of frameworks into other frameworks or condensed structures. The NASA-funded research described in this report focuses to varying degrees on all of the above issues and has been described in several publications. Following is the presentation of the highlights of our current research program. The report is divided into five sections: (1) Fundamental aspects of the crystal growth process; (2) Morphological and Surface properties of crystals; (3) Crystal dissolution and transformations; (4) Modeling of Crystal Growth; (5) Relevant Microgravity Experiments.
This talk will focus on photonic bandgaps that arise due to nearly free photon and tight-binding effects in coupled microparticle and ring-resonator systems. The Mie formulation for homogeneous spheres is generalized to handle core/shell systems and multiple concentric layers in a manner that exploits an analogy with stratified planar systems, thereby allowing concentric multi-layered structures to be treated as photonic bandgap (PBG) materials. Representative results from a Mie code employing this analogy demonstrate that photonic bands arising from nearly free photon effects are easily observed in the backscattering, asymmetry parameter, and albedo for periodic quarter-wave concentric layers, though are not readily apparent in extinction spectra. Rather, the periodicity simply alters the scattering profile, enhancing the ratio of backscattering to forward scattering inside the bandgap, in direct analogy with planar quarter-wave multilayers. PBGs arising from tight-binding may also be observed when the layers (or rings) are designed such that the coupling between them is weak. We demonstrate that for a structure consisting of N coupled micro-resonators, the morphology dependent resonances split into N higher-Q modes, in direct analogy with other types of oscillators, and that this splitting ultimately results in PBGs which can lead to enhanced nonlinear optical effects.
The first undercooling nucleation measurements of electrostatic-levitated droplets of TiZrNi alloys that form the icosahedral quasicrystal phase (i-phase) are presented. The reduced undercooling for crystallization decreases with an increasing polytetrahedral order of the primary solidifying phase, supporting the existence of a developing icosahedral short-range order in the undercooled liquid. X-ray diffraction measurements made at the Advance Photon Source on levitated liquid droplets of these alloys at their liquidus temperatures, however, show no evidence for increased icosahedral order. This suggests that significant ordering only occurs below the melting temperature.
High quality CdTe crystals with resistivities higher than 10(exp 8) omega cm were grown by the physical vapor transport technique. Indium, Aluminum, and the transition metal Scandium were introduced at the nominal level of about 6 ppm to the source material. Low-temperature photoluminescence (PL) has been employed to identify the origins of PL emissions of the crystals. The emission peaks at 1.584 eV and 1.581 eV were found only in the In-doped crystal. The result suggests that the luminescence line at 1.584 eV is associated with Cd-vacancy/indium complex. The intensity of the broadband centered at 1.43 eV decreases strongly with introduction of Sc.
Including the capability to induce a controlled fluid flow in the melt can significantly enrich research on solidification phenomena in a microgravity environment. The traveling magnetic field (TMF) is a promising technique to achieve this goal and is the aim of our ground-based project. In this presentation we will discuss new theoretical as well as experimental results recently obtained by our group. In particular, we experimentally demonstrated efficient mixing of metal alloys in long tubes subjected to TMF during processing. Application of this technique can provide an elegant solution to ensure melt homogenization prior to solidification in a microgravity environment where natural convection is generally absent. Results of our experimental work of applying the TMF technique to alloy melts will be presented. Possible applications of TMF on board the International Space Station will also be discussed.
It is highly desirable to have a non-nuclear power rich option for the human exploration of Mars. Utilizing a Solar Electric Propulsion, SEP, / Power Beaming architecture for a non-nuclear power option for a human Mars base potentially avoids the weather and dust sensitivities of the surface photovoltaic option. Further from Mars areosynchronous orbit near year round power can be provided. Mission analysis, however, concludes that ultra high (245 GHz) frequencies or laser transmission technologies are required for Mars landed mass competitiveness with the surface photovoltaic option if the receiving rectifying antenna "rectenna" is transported from Earth. It is suggested in this paper that producing rectenna in situ on Mars surface might make a more conventional 5.8 GHz system competitive with surface PV. The premium of a competitive, robust, continuous base power might make the development of a 10 plus MWe class SEP for human Mars mission a more attractive non-nuclear option.
It is well known that irregular eutectics such as Al-Si and Fe-C exhibit larger lamellar spacings and undercoolings compared to the predictions made by the Jackson and Hunt (JH) theory. In this paper, we reexamine the JH theory and relax some of the assumptions used in that treatment. The modified theoretical model has enhanced capabilities to predict the lamellar spacing in both regular and irregular eutectics. For the Al-Si system in particular we identified two different spacing selection mechanisms:a) for a particular growth rate, a nearly isothermal interface can be achieved at a unique minimum spacing lambda(sub I); b) the average spacing in the microstructure (lambda(sub av) greater than lambda(sub I)) is essentially dictated by the undercooling of the faceted phase. Based on the modified theoretical model a semi-empirical expression has been developed to account for the influence of the temperature gradient. Application of a Mullin and Sekerka type stability analysis for eutectics will also be presented and the results compared to the modified JH model. It will be shown that the both theoretical approaches are in good agreement with each other and also with the published experimental measurements.
There are many ways of judging a good crystal. Which we use depends on the qualities we seek. For gemstones size, clarity and impurity levels (color) are paramount. For the semiconductor industry purity is probably the most important quality. For the structural crystallographer the primary desideratum is the somewhat more subtle concept of internal order. In this chapter we discuss the effect of internal order (or the lack of it) on the crystal's diffraction properties.
A Hg0.84Zn0.16Te alloy crystal was back-melted and partially resolidified during the first United States Microgravity Laboratory (USML-1) mission in the Marshall Space Flight Center's Crystal Growth Furnace. The experiment was inadvertently terminated at about 30% of planned completion. Nonetheless, it was successfully demonstrated that a HgZnTe alloy ingot partially grown and quenched on the ground can be back-melted and regrown in space under nearly steady state growth conditions. An identical "groundtruth" experiment was performed following the mission and a comparison between the properties of the crystals is described. The results indicate the importance of residual microgravity acceleration (approx. less than 0.4 mg) even in the sub-microgravity range for the slow solidification velocities and large density gradients.
Predicting the occurrence of human cancer following exposure to any agent causing genetic damage is a difficult task. This is because the uncertainty of uniform exposure to the damaging agent, and the uncertainty of uniform processing of that damage within a complex set of biological variables, degrade the confidence of predicting the delayed expression of cancer as a relatively rare event within any given clinically normal individual. The radiation health research priorities for enabling long-duration human exploration of space were established in the 1996 NRC Report entitled 'Radiation Hazards to Crews of Interplanetary Missions: Biological Issues and Research Strategies'. This report emphasized that a 15-fold uncertainty in predicting radiation-induced cancer incidence must be reduced before NASA can commit humans to extended interplanetary missions. That report concluded that the great majority of this uncertainty is biologically based, while a minority is physically based due to uncertainties in radiation dosimetry and radiation transport codes. Since that report, the biologically based uncertainty has remained large, and the relatively small uncertainty associated with radiation dosimetry has increased due to the considerations raised by concepts of microdosimetry. In a practical sense, however, the additional uncertainties introduced by microdosimetry are encouraging since they are in a direction of lowered effective dose absorbed through infrequent interactions of any given cell with the high energy particle component of space radiation. Additional information is contained in the original extended abstract.
Using particle image velocimetry we have measured the sedimentation dynamics of non-Brownian spheres over a wide range of Reynolds numbers (Re) between 0.001 and 2.5. Particle velocity fluctuations about the mean settling velocity show large-scale correlations whose spatial extent and magnitude Delta V/V are independent of Re up to a critical value Re less than Re(sub c). For Re greater than Re(sub c) the fluctuations substantially diminish with increasing Reynolds number due to inertial screening of the long-range hydrodynamic interactions (HI). The onset of inertial affects is found to occur when the Oseen length l(sub o)=v/V becomes of order the correlation length. In the inertial regime, the velocity fluctuations follow -(Delta V/V)(sup 2) approaching ln(Re), in agreement with an integration of the (l/r) HI over a narrow region extending up to the Oseen length l(sub o). A simple "blob" model connects the measured correlation lengths to the magnitudes of the velocity fluctuations.
The Enhanced Gaseous Nitrogen (EGN) Dewar is a cryogenic dry shipper with a sealed cylinder inserted inside along with a temperature-monitoring device, and is intended for macromolecular crystallization experiments on the International Space Station. Within the Dewar, each crystallization experiment is contained as a solution within a plastic capillary. The standard procedure for loading samples in these tubes has involved rapid freezing of the precipitant and biomolecule solution directly in liquid nitrogen; this method, however, often results in uncontrolled formation of air voids. These air pockets, or bubbles, then can lead to irreproducible crystallization results. A novel protocol has been developed to prevent formation of bubbles, and this has been tested in the laboratory as well as aboard the International Space Station during a 42-day long mission of July/August of 2001. Furthermore, gain or loss of mass from solutions within the capillaries revealed that mass transport amongst separated tubes occurred, and that this mass transport was determined by the hygroscopic character of a solution contained in any given tube. The sample volume and the surface area of the plastic capillary tube also related to the observed mass transport.
The Mie formulation for homogeneous spheres is generalized to handle concentric multilayers in a manner that exploits an analogy with stratified planar systems, enabling these structures to be treated as photonic bandgap materials.