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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.

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At least 145 records · Page 8
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NASA NTRS1988

Morphological evolution of growing crystals - A Monte Carlo simulation

The combined effects of nutrient diffusion and surface kinetics on the crystal morphology were investigated using a Monte Carlo model to simulate the evolving morphology of a crystal growing from a two-component gaseous nutrient phase. The model combines nutrient diffusion, based on a modified diffusion-limited aggregation process, with anisotropic surface-attachment kinetics and surface diffusion. A variety of conditions, ranging from kinetic-controlled to diffusion-controlled growth, were examined. Successive transitions from compact faceted (dominant surface kinetics) to open dendritic morphologies (dominant volume diffusion) were obtained.

Xiao, Rong-Fu↗
NASA NTRS2003

Modeling Tetragonal Lysozyme Crystal Growth Rates

Tetragonal lysozyme 110 face crystal growth rates, measured over 5 orders of magnitude in range, can be described using a model where growth occurs by 2D nucleation on the crystal surface for solution supersaturations of c/c(sub eq) less than or equal to 7 +/- 2. Based upon the model, the step energy per unit length, beta was estimated to be approx. 5.3 +/- 0.4 x 10(exp -7) erg/mol-cm, which for a step height of 56 A corresponds to barrier of approx. 7 +/- 1 k(sub B)T at 300 K. For supersaturations of c/c(sub eq) > 8, the model emphasizing crystal growth by 2D nucleation not only could not predict, but also consistently overestimated, the highest observable crystal growth rates. Kinetic roughening is hypothesized to occur at a cross-over supersaturation of c/c(sub eq) > 8, where crystal growth is postulated to occur by a different process such as adsorption. Under this assumption, all growth rate data indicated that a kinetic roughening transition and subsequent crystal growth by adsorption for all solution conditions, varying in buffer pH, temperature and precipitant concentration, occurs for c/c(sub eq)(T, pH, NaCl) in the range between 5 and 10, with an energy barrier for adsorption estimated to be approx. 20 k(sub B)T at 300 K. Based upon these and other estimates, we determined the size of the critical surface nucleate, at the crossover supersaturation and higher concentrations, to range from 4 to 10 molecules.

Gorti, Sridhar↗
NASA NTRS2004

Kinetic Roughening Transition and Energetics of Tetragonal Lysozyme Crystal Growth

Interpretation of lysozyme crystal growth rates using well-established physical theories enabled the discovery of a phenomenon possibly indicative of kinetic roughening. For example, lysozyme crystals grown above a critical supersaturation sigma, (where supersaturation sigma = ln c/c(sub eq), c = the protein concentration and c(sub eq) = the solubility concentration) exhibit microscopically rough surfaces due to the continuous addition of growth units anywhere on the surface of a crystal. The rate of crystal growth, V(sub c), for the continuous growth process is determined by the continuous flux of macromolecules onto a unit area of the crystal surface, a, from a distance, xi, per unit time due to diffusion, and a probability of attachment onto the crystal surface, expressed. Based upon models applied, the energetics of lysozyme crystal growth was determined. The magnitudes of the energy barriers of crystal growth for both the (110) and (101) faces of tetragonal lysozyme crystals are compared. Finally, evidence supportive of the kinetic roughening hypothesis is presented.

Gorti, Sridhar↗
NASA NTRS1994

Convective flow effects on protein crystal growth

A high-resolution microscopic interferometric setup for the monitoring of protein morphologies has been developed. Growth or dissolution of a crystal can be resolved with a long-term depth resolution of 200 A and a lateral resolution of 2 microns. This capability of simultaneously monitoring the interfacial displacement with high local depth resolution has yielded several novel results. We have found with lysozyme that (1) the normal growth rate is oscillatory, and (2) depending on the impurity content of the solution, the growth step density is either greater or lower at the periphery of a facet than in its center. The repartitioning of Na plus and Cl minus ions between lysozyme solutions and crystals was studied for a wide range of crystallization conditions. A nucleation-growth-repartitioning model was developed, to interpret the large body of data in unified way. The results strongly suggest that (1) the ion to lysozyne ratio in the crystal depends mostly on kinetic rather than crystallographic parameters, and (2) lysozyme crystals possess a salt-rich core with a diameter electron microscopy results appear to confirm this finding, which could have far-reaching consequences for x-ray diffraction studies. A computational model for diffusive-convective transport in protein crystallization has been applied to a realistic growth cell geometry, taking into account the findings of the above repartitioning studies and our kinetics data for the growth of lysozyme. The results show that even in the small cell employed, protein concentration nonuniformities and gravity-driven solutal convection can be significant. The calculated convection velocities are of the same order to magnitude as those found in earlier experiments. As expected, convective transport, i.e., at Og, lysozyme crystal growth remains kinetically limited. The salt distribution in the crystal is predicted to be non-uniform at both 1g and 0g, as a consequence of protein depletion in the solution. Static and dynamic light scattering studies in undersaturated and supersaturated solutions have been performed. Diffusivities in undersaturated solutions, were found to vary with lysozyme concentrations. Depending on the salt concentration, the diffusivities either increase or decrease. Interestingly, the corresponding static scattering intensities behave oppositely, Our current analysis indicates that these changes are inconsistent with aggregation in undersaturated solutions. However, the data are compatible with concentration-dependent changes of the interactions between protein and salt.

Rosenberger, Franz↗
NASA NTRS2005

Inorganic and Protein Crystal Assembly in Solutions

The basic kinetic and thermodynamic concepts of crystal growth will be revisited in view of recent AFM and interferometric findings. These concepts are as follows: 1) The Kossel crystal model that allows only one kink type on the crystal surface. The modern theory is developed overwhelmingly for the Kessel model; 2) Presumption that intensive step fluctuations maintain kink density sufficiently high to allow applicability of Gibbs-Thomson law; 3) Common experience that unlimited step bunching (morphological instability) during layer growth from solutions and supercooled melts always takes place if the step flow direction coincides with that of the fluid.

Chernov, A. A.↗
NASA NTRS1979

Crystallization, flow and thermal histories of lunar and terrestrial compositions

Contents: a kinetic treatment of glass formation; effects of nucleating heterogeneities on glass formation; glass formation under continuous cooling conditions; crystallization statistics; kinetics of crystal nucleation; diffusion controlled crystal growth; crystallization of lunar compositions; crystallization between solidus and liquidus; crystallization on reheating a glass; temperature distributions during crystallization; crystallization of anorthite and anorthite-albite compositions; effect of oxidation state on viscosity; diffusive creep and viscous flow; high temperature flow behavior of glass-forming liquids, a free volume interpretation; viscous flow behavior of lunar compositions; thermal history of orange soil material; breccias formation by viscous sintering; viscous sintering; thermal histories of breccias; solute partitioning and thermal history of lunar rocks; heat flow in impact melts; and thermal histories of olivines.

Uhlmann, D. R.↗
NASA NTRS1989

Effects of crystal-melt interfacial energy anisotropy on dendritic morphology and growth kinetics

Morphological and kinetic studies of succinonitrile, a BCC crystal with a low (0.5 percent) anisotropy and pivalic acid, and FCC crystal with relatively large (5 percent) anisotropy in solid-liquid interfacial energy, show clearly that anisotropy in the solid-liquid interfacial energy does not affect the tip radius-velocity relationship, but has a profound influence on the tip region and the rate of amplification of branching waves. Anisotropy of the solid-liquid interfacial energy may be one of the key factors by which the microstructural characteristics of cast structures reflect individual material behavior, especially crystal symmetry.

Glicksman, M. E.↗
NASA NTRS1991

Growth kinetics of physical vapor transport processes: Crystal growth of the optoelectronic material mercurous chloride

Physical vapor transport processes were studied for the purpose of identifying the magnitude of convective effects on the crystal growth process. The effects of convection on crystal quality were were studied by varying the aspect ratio and those thermal conditions which ultimately affect thermal convection during physical vapor transport. An important outcome of the present study was the observation that the convection growth rate increased up to a certain value and then dropped to a constant value for high aspect ratios. This indicated that a very complex transport had occurred which could not be explained by linear stability theory. Better quality crystals grown at a low Rayleigh number confirmed that improved properties are possible in convectionless environments.

Singh, N. B.↗
NASA NTRS1997

Unsteady Crystal Growth Due to Step-Bunch Cascading

Based on our experimental findings of growth rate fluctuations during the crystallization of the protein lysozym, we have developed a numerical model that combines diffusion in the bulk of a solution with diffusive transport to microscopic growth steps that propagate on a finite crystal facet. Nonlinearities in layer growth kinetics arising from step interaction by bulk and surface diffusion, and from step generation by surface nucleation, are taken into account. On evaluation of the model with properties characteristic for the solute transport, and the generation and propagation of steps in the lysozyme system, growth rate fluctuations of the same magnitude and characteristic time, as in the experiments, are obtained. The fluctuation time scale is large compared to that of step generation. Variations of the governing parameters of the model reveal that both the nonlinearity in step kinetics and mixed transport-kinetics control of the crystallization process are necessary conditions for the fluctuations. On a microscopic scale, the fluctuations are associated with a morphological instability of the vicinal face, in which a step bunch triggers a cascade of new step bunches through the microscopic interfacial supersaturation distribution.

Vekilov, Peter G.↗
NASA NTRS1976

Rise kinetics of light-induced modulation of absorption for a CdS crystal

An experimental study has been made of the rise kinetics for changes in optical absorption in a single crystal of CdS which was bulk excited by pulsed laser light. The experimental data were compared to calculations from a simple model involving a bimolecular process. Experimental and calculated values agreed to within the experimental error and confirmed that light-induced modulation of absorption is a bimolecular process.

Long, E. R., Jr.↗
NASA NTRS2003

Step Bunch Evolution on Vicinal Faces of KDP

For in-situ studies of the formation and evolution of step patterns in solution growth, we have assembled an experimental setup based on Michelson interferometry with the growing crystal surface as one of the reflective surfaces. The device allows data collection over a relatively large area (approximately 4 sq. mm) in situ and in real time during growth. The depth resolution is improved over traditional interferometry using phase-shifted images combining by a suitable algorithm. We achieve a depth resolution of approximately 50 Angstroms. Lateral resolution, dependent on the degree of magnification, is around 0.3 to 5 microns. The crystal chosen as a model in this work is potassium dihydrogen phosphate (KDP), the optically non-linear material widely used in frequency doubling applications. Kinetics of KDP crystallization is well studied so that KDP can serve as a benchmark for our investigations. We present quantitative results on the onset, initial stages and development of instabilities in moving step trains on vicinal crystal surfaces at varying supersaturation, flow rate, and flow direction. The kinetics data suggest that at low supersaturations, step bunching is caused by impurity retardation of the steps, while at higher supersaturations, we link the non-linearity during growth to interdependence of the velocity and density of the steps evidenced in independent experiments. The behavior on the surface is very dynamic, small bunches both merge and split from larger bunches as they travel across the facet. We present evidence that despite these dynamics, under steady conditions there exists a limiting value to step bunch height. This height is reached at distances between 600 and 1000 microns from the step source. In our experiments, we observed the retention of this step bunch height limit up to the path of 1500 microns.

Booth, N. A.↗
NASA NTRS2004

Kinetic Roughening and Energetics of Tetragonal Lysozyme Crystal Growth: A Preliminary Atomic Force Microscopy Investigation

We examined particulars of crystal growth from measurements obtained at both microscopic and molecular levels. The crystal growth measurements performed at the microscopic level are well characterized by a model that balances the flux of macromolecules towards the crystal surface with the flux of the crystal surface. Numerical evaluation of model with measurements of crystal growth, in time, provided accurate estimates for the average growth velocities. Growth velocities thus obtained were also interpreted using well-established phenomenological theories. Moreover, we find that microscopic measurements of growth velocity measurements obtained as a function of temperature best characterizes changes in crystal growth modes, when present. We also examined the possibility of detecting a change in crystal growth modes at the molecular level using atomic force microscopy, AFM. From preliminary AFM measurements performed at various supersaturations, we find that magnitude of surface height fluctuations, h(x), increases with supersaturation. Further examination of surface height fluctuations using methods established for fluctuation spectroscopy also enabled the discovery of the existence of a characteristic length, c, which may possibly determine the mode of crystal growth. Although the results are preliminary, we establish the non- critical divergence of 5 and the root-mean-square (rms) magnitude of height-height fluctuations as the kinetic roughening transition temperatures are approached. Moreover, we also examine approximate models for interpreting the non-critical behavior of both 6 and rms magnitude of height-height fluctuations, as the solution supersaturation is increased towards the kinetic roughening supersaturation.

Gorti, Sridhar↗
NASA NTRS2004

Protein Crystals and their Growth

Recent results on binding between protein molecules in crystal lattice, crystal-solution surface energy, elastic properties and strength and spontaneous crystal cracking are reviewed and discussed in the first half of this paper (Sea 2-4). In the second par&, some basic approaches to solubility of proteins are followed by overview on crystal nucleation and growth (Sec 5). It is argued that variability of mixing in batch crystallization may be a source for scattering of crystal number ultimately appearing in the batch. Frequency at which new molecules join crystal lattice is measured by kinetic coefficient and related to the observable crystal growth rate. Numerical criteria to discriminate diffusion and kinetic limited growth are discussed on this basis in Sec 7. In Sec 8, creation of defects is discussed with the emphasis on the role of impurities and convection on macromolecular crystal I;erfection.

Chernov, A. A.↗
NASA NTRS1994

Convective flow effects on protein crystal growth

The long-term stability of the interferometric setup for the monitoring of protein morphologies has been improved. Growth or dissolution of a crystal on a 100 A scale can now be clearly distinguished from dimensional changes occurring within the optical path of the interferometer. This capability of simultaneously monitoring the local interfacial displacement at several widely-spaced positions on the crystal surface with high local depth resolution, has already yielded novel results. We found with lysozyme that (1) the normal growth rate is oscillatory, and (2) the mean growth step density is greater at the periphery of a facet than in its center. The repartitioning of Na(+) and Cl(-) ions between lysozyme solutions and crystals was studied for a wide range of crystallization conditions. A nucleation-growth-repartitioning model was developed to interpret the large body of data in a unified way. The results strongly suggests that (1) the ion to lysozyme ratio in the crystal depends mostly on kinetic rather than crystallographic parameters, and (2) lysozyme crystals possess a salt-rich core with a diameter on the order of 10 microns. The computational model for diffusive-convective transport in protein crystallization (see the First Report) has been applied to a realistic growth cell geometry, taking into account the findings of the above repartitioning studies. These results show that some elements of a moving boundary problem must be incorporated into the model in order to obtain a more realistic description. Our experimental setup for light scattering investigations of aggregation and nucleation in protein solutions has been extensively tested. Scattering intensity measurements with a true Rayleigh scatterer produced systematically increased forward scattering, indicating problems with glare. These have been resolved. Preliminary measurements with supersaturated lysozyme solutions revealed that the scatterers grow with time. Work has begun on a computer program for the unified evaluation of simultaneously obtained, multi-angle static and dynamic light scattering data.

Rosenberger, Franz↗
NASA NTRS1988

Two puzzling aspects of protein crystal growth

A study is presented of several mechanisms which may reduce crystal growth rates and or terminate crystal growth. It is found that salt gradients which change the local chemical potential of the protein are insufficient to account for the slow crystal growth rates which have been reported. Contaminants which adsorb protein from solution may reduce the effective protein concentration, but the impurity's concentration and its affinity for protein are unknown. Association of protein molecules in bulk solution can reduce the monomer concentration significantly, but extant theory and experiment are not sensitive enough to determine the actual concentration of aggregates in solution. For systems of interest, shear-induced effects were found to be too weak to interfere with normal binding of incoming protein molecules. Although we found that most crystal growth occurs in a regime where both interfacial kinetics and diffusion influence crystal growth, the role of mass transfer rates on the terminal size of crystals is unknown, primarily because no data exist which cover the size range of interest (0.1 mm to 1 mm in length).

Grant, M. L.↗
NASA NTRS1989

Novel polyimide compositions based on 4,4': Isophthaloyldiphthalic anaydride (IDPA)

A series of twelve high temperature, high performance polyimide compositions based on 4,4'-isophthaloyl diphthalic anhydride (IDPA) was prepared and characterized. Tough, film-forming, organic solvent-insoluble polyimides were obtained. Three materials were semicrystalline. Several gave excellent long-term thermooxidative stability by isothermal thermogravimetric analysis (ITGA) at 300 C and 350 C in air when compared to Kapton H film (duPont). One extensively studied material displayed different levels of semicrystallinity over a wide range of final cure time/temperatures. The polyimide from IDPA and 1,3-bis (4-aminophenoxy 4'-benzoyl) benzene exhibited multiple crystallization and melting behavior, implying the existence of two kinetic and two thermodynamic crystallization and melting transitions by differential scanning calorimetry (DSC).

Pratt, J. Richard↗