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NASA NTRS1994

Kinetics of phase transformation in glass forming systems

The objectives of this research were to (1) develop computer models for realistic simulations of nucleation and crystal growth in glasses, which would also have the flexibility to accomodate the different variables related to sample characteristics and experimental conditions, and (2) design and perform nucleation and crystallization experiments using calorimetric measurements, such as differential scanning calorimetry (DSC) and differential thermal analysis (DTA) to verify these models. The variables related to sample characteristics mentioned in (1) above include size of the glass particles, nucleating agents, and the relative concentration of the surface and internal nuclei. A change in any of these variables changes the mode of the transformation (crystallization) kinetics. A variation in experimental conditions includes isothermal and nonisothermal DSC/DTA measurements. This research would lead to develop improved, more realistic methods for analysis of the DSC/DTA peak profiles to determine the kinetic parameters for nucleation and crystal growth as well as to assess the relative merits and demerits of the thermoanalytical models presently used to study the phase transformation in glasses.

Ray, Chandra S.↗

NASA NTRS2014

Properties of Desert Sand and CMAS Glass

As-received desert sand from a Middle East country has been characterized for its phase composition and thermal stability. X-ray diffraction analysis showed the presence of quartz (SiO2), calcite (CaCO3), gypsum (CaSO4.2H2O), and NaAlSi3O8 phases in as-received desert sand and showed weight loss of approx. 35 percent due to decomposition of CaCO3 and CaSO4.2H2O when heated to 1400 C. A batch of as-received desert sand was melted into calcium magnesium aluminosilicate (CMAS) glass at approx. 1500 C. From inductively coupled plasma-atomic emission spectrometry, chemical composition of the CMAS glass was analyzed to be 27.8CaO-4MgO-5Al2O3-61.6SiO2-0.6Fe2O3-1K2O (mole percent). Various physical, thermal and mechanical properties of the glass have been evaluated. Bulk density of CMAS glass was 2.69 g/cc, Young's modulus 92 GPa, Shear modulus 36 GPa, Poisson's ratio 0.28, dilatometric glass transition temperature (T (sub g)) 706 C, softening point (T (sub d)) 764 C, Vickers microhardness 6.3 +/- 0.4 GPa, indentation fracture toughness 0.75 +/- 0.15 MPa.m (sup 1/2), and coefficient of thermal expansion (CTE) 9.8 x 10 (exp -6)/degC in the temperature range 25 to 700 C. Temperature dependence of viscosity has also been estimated from various reference points of the CMAS glass using the Vogel-Fulcher-Tamman (VFT) equation. The glass remained amorphous after heat treating at 850 C for 10 hr but crystallized into CaSiO3 and Ca-Mg-Al silicate phases at 900 C or higher temperatures. Crystallization kinetics of the CMAS glass has also been investigated by differential thermal analysis (DTA). Activation energies for the crystallization of two different phases in the glass were calculated to be 403 and 483 kJ/mol, respectively.

Desert sand↗

NASA NTRS1996

Computer Modeling of Non-Isothermal Crystallization

A realistic computer model for simulating isothermal and non-isothermal phase transformations proceeding by homogeneous and heterogeneous nucleation and interface-limited growth is presented. A new treatment for particle size effects on the crystallization kinetics is developed and is incorporated into the numerical model. Time-dependent nucleation rates, size-dependent growth rates, and surface crystallization are also included. Model predictions are compared with experimental measurements of DSC/DTA peak parameters for the crystallization of lithium disilicate glass as a function of particle size, Pt doping levels, and water content. The quantitative agreement that is demonstrated indicates that the numerical model can be used to extract key kinetic data from easily obtained calorimetric data. The model can also be used to probe nucleation and growth behavior in regimes that are otherwise inaccessible. Based on a fit to data, an earlier prediction that the time-dependent nucleation rate in a DSC/DTA scan can rise above the steady-state value at a temperature higher than the peak in the steady-state rate is demonstrated.

Kelton, K. F.↗

NASA NTRS1996

Crystallization of amorphous water ice in the solar system

Electron diffraction studies of vapor-deposited water ice have characterized the dynamical structural changes during crystallization that affect volatile retention in cometary materials. Crystallization is found to occur by nucleation of small domains, while leaving a significant part of the amorphous material in a slightly more relaxed amorphous state that coexists metastably with cubic crystalline ice. The onset of the amorphous relaxation is prior to crystallization and coincides with the glass transition. Above the glass transition temperature, the crystallization kinetics are consistent with the amorphous solid becoming a "strong" viscous liquid. The amorphous component can effectively retain volatiles during crystallization if the volatile concentration is approximately 10% or less. For higher initial impurity concentrations, a significant amount of impurities is released during crystallization, probably because the impurities are trapped on the surfaces of micropores. A model for crystallization over long timescales is described that can be applied to a wide range of impure water ices under typical astrophysical conditions if the fragility factor D, which describes the viscosity behavior, can be estimated.

NASA Center ARC↗

NASA NTRS1985

A study of the applicability of nucleation theory to quasi-thermodynamic transformations of second and higher Ehrenfest-order

Transient and steady-state phenomena in temperature, stress, and electric, field intensity in ferroelectric polymers were investigated. The application and extension of the theory in the primary stage to the polarization domain nucleation and growth in ferroelectric polymers were developed. The kinetics of this growth were investigated. Expressions describing nucleation under the influence of an electric field were found through the expansion of the Gibbs' free energy in a Maclaurin series. The series was expanded in the electric field strength rather than the degree of undercooling. The resulting expressions were manipulated and applied to the case of nucleation of polarized domains in ferroelectric polymers. The kinetics of the nucleation and growth of polarized domains are also investigated. This was accomplished through the modification of the Johnson-Mehl-Avrami treatment of crystallization kinetics to be applicable to the growth of polarization domains in ferroelectric materials.

Barker, R. E., Jr.↗

NASA NTRS1986

Crystallization of baria-titania-silica glasses

The critical cooling rate for glass formation, Rc, and the crystallization kinetics of the compositions (1/2)(100-x)BaO-(1/2)(100-x)TiO2-(x)SiO2 with x = 20, 25, 30, 33.3, and 40 mol pct were studied using a thermal image furnace. Crystallization was studied under nonisothermal conditions, and the data were analyzed using the Johnson-Mehl-Avrami equation. The Rc and activation energy for crystallization both decrease with increasing silica content. Fresnoite, Ba2TiSi2O8, crystallized from all of the glasses when they were reheated. The infrared absorption spectra of the glasses and crystals show that they both contain (Si2O7) and square pyramidal (TiO5) groups.

Ray, Chandra S.↗

NASA NTRS2001

The Vitrification and Determination of the Crystallization Time Scales of a Zr58.5Nb2.8Cu15.6Ni12.8Al10.3 Bulk Metallic Glass Forming Liquid

Zr58.5Nb2.8Cul5.6Nil2.8All0.3 is the first bulk glass forming liquid that does not contain beryllium to be vitrified by purely radiative cooling in the containerless electrostatic levitation process. The measured critical cooling rate is 1.75 K/s. The sluggish crystallization kinetics enable the determination of the time-temperature-transformation (TTT) diagram between the liquidus and the glass transition temperatures. At the nose of the TTT diagram, the shortest time to reach crystallization in an isothermal experiment is 32 seconds. In contrast to other bulk metallic glasses the scatter in the crystallization onset times are small at both high and low temperatures.

Hays, C. C.↗

NASA NTRS1988

Apparatus for rapid thermal analysis studies of reluctant glass formers

An apparatus is described for performing rapid thermal analysis of milligram quantities of reluctant glass formers. Nucleation and crystallization kinetic analysis on samples cooled at very rapid cooling rates of 10 to 2500 C/s is described. The apparatus utilizes focused heating of a sample contained on a fine thermocouple. The measured times and temperatures for nucleation of crystallization at various cooling rates and experimental conditions permit the construction of continuous cooling crystallization boundaries and the determination of critical cooling rates for glass formation.

Ethridge, Edwin C.↗

NASA NTRS1998

Intrinsic Kinetics Fluctuations as Cause of Growth Inhomogeneity in Protein Crystals

Intrinsic kinetics instabilities in the form of growth step bunching during the crystallization of the protein lysozyme from solution were characterized by in situ high-resolution optical interferometry. Compositional variations (striations) in the crystal, which potentially decrease its utility, e.g., for molecular structure studies by diffraction methods, were visualized by polarized light reflection microscopy. A spatiotemporal correlation was established between the sequence of moving step bunches and the striations.

Vekilov, Peter G.↗

NASA NTRS1998

The Growth of Protein Crystals Using McDUCK

Most of the current microgravity crystal growth hardware is optimized to produce crystals within the limited time available on orbit. This often results in the actual nucleation and growth process being rushed or the system not coming to equilibrium within the limited time available. Longer duration hardware exists, but one cannot readily pick out crystals grown early versus those which nucleated and grew more slowly. We have devised a long duration apparatus, the Multi-chamber Dialysis Unit for Crystallization Kinetics, or McDUCK. This apparatus-is a series of protein chambers, stacked upon a precipitant reservoir chamber. All chambers are separated by a dialysis membrane, which serves to pass small molecules while retaining the protein. The volume of the Precipitant chamber is equal to the sum of the volumes of the protein chamber. In operation, the appropriate chambers are filled with precipitant solution or protein solution, and the McDUCK is placed standing upright, with the precipitant chamber on the bottom. The precipitant diffuses upwards over time, with the time to reach equilibration a function of the diffusivity of the precipitant and the overall length of the diffusion pathway. Typical equilibration times are approximately 2-4 months, and one can readily separate rapid from slow nucleation and growth crystals. An advantage on Earth is that the vertical precipitant concentration gradient dominates that of the solute, thus dampening out solute density gradient driven convective flows. However, large Earth-grown crystals have so far tended to be more two dimensional. Preliminary X-ray diffraction analysis of lysozyme crystals grown in McDUCK have indicated that the best, and largest, come from the middle chambers, suggesting that there is an optimal growth rate. Further, the improvements in diffraction resolution have been better signal to noise ratios in the low resolution data, not an increase in resolution overall. Due to the persistently large crystals grown we are currently proposing McDUCK for the growth of macromolecule crystals for use in neutron diffraction studies.

Ewing, Felicia↗

NASA NTRS1979

Effects of isothermal and cyclic exposures on interface structure and mechanical properties of FPalpha-Al2O3/aluminum composites

The microstructural and interface stability of FPalpha-Al203/Al-Li composites are investigated as a function of isothermal exposure at 500 C or thermal cycling between 140 and 500 C with hold time at Tmax. Interfacial morphology, growth kinetics, crystal structure, and composition of interfacial reaction products are characterized. Strength is monitored in the transverse orientation, and fracture mechanics is analyzed in terms of interface reaction products. The interfacial reaction product in FP/Al is Li2O.5Al2O3. Significant fiber-matrix reaction occurs during fabrication. The number of thermal cycles rather than total time at Tmax is the determining factor in strength degradation, thermal cycling giving rise to voids at the fiber-matrix interface. Extensive interface failures occur at composite fracture stresses below about 128 MPa; above this stress level failure is attributed to ductile matrix fracture.

Kim, W. M.↗

NASA NTRS1990

LaRC TPI 1500 series polymers

The crystallization behavior and the melt flow properties of two batches of 1500 series LaRC-TPI polymers from Mitsui Toatsu Chemicals (MTC) were investigated. The characterization methods include Differential Scanning Calorimetry, the x ray diffractography and the melt rheology. The as-received materials possess initial crystalline melting peak temperatures of 295 and 305 C, respectively. These materials are less readily recrystallizable at elevated temperatures when compared to other semicrystalline thermoplastics. For the samples annealed at temperatures below 330 C, a semicrystalline polymer can be obtained. On the other hand, a purely amorphous structure is realized in the samples annealed at temperatures above 330 C. Isothermal crystallization kinetics were studied by means of the simple Avrami equation. The viscoelastic properties at elevated temperatures below and above glass transition temperature of the polymers were measured. Information with regard to the molecule sizes and distributions in these polymers were also extracted from melt rheology.

Hou, Tan-Hung↗

NASA NTRS1990

Superconducting Bi(1.5)Pb(0.5)Sr2Ca2Cu3O(x) ceramics by rapid melt quenching and glass crystallization

The preparation of superconducting Bi(1.5)Pb(0.5)Sr2Ca2Cu3O(x) in the glassy state is described, and the results of a study of its crystallization kinetics are presented. The annealing parameters for transforming the glass into a superconductor containing a large fraction of the high-Tc phase were determined. It was found that prolonged annealing (longer than 10 days) in air at 840 C, followed by slow cooling, results in the Tc of 107.2 K and a sharp transition of 2 K.

Bansal, Narottam P.↗

NASA NTRS1998

Volume Diffusion Growth Kinetics and Step Geometry in Crystal Growth

The role of step geometry in two-dimensional stationary volume diff4sion process used in crystal growth kinetics models is investigated. Three different interface shapes: a) a planar interface, b) an equidistant hemispherical bumps train tAx interface, and c) a train of right angled steps, are used in this comparative study. The ratio of the super-saturation to the diffusive flux at the step position is used as a control parameter. The value of this parameter can vary as much as 50% for different geometries. An approximate analytical formula is derived for the right angled steps geometry. In addition to the kinetic models, this formula can be utilized in macrostep growth models. Finally, numerical modeling of the diffusive and convective transport for equidistant steps is conducted. In particular, the role of fluid flow resulting from the advancement of steps and its contribution to the transport of species to the steps is investigated.

Mazuruk, Konstantin↗

NASA NTRS2004

Low Gravity Rapid Thermal Analysis of Glass

It has been observed by two research groups that ZrF4-BaF2-LaF3-AlF3-NaF (ZBLAN) glass crystallization is suppressed in microgravity. The mechanism for this phenomenon is unknown at the present time. In order to better understand the mechanism, an experiment was performed on NASA's KC135 reduced gravity aircraft to obtain quantitative crystallization data. An apparatus was designed and constructed for performing rapid thermal analysis of milligram quantities of ZBLAN glass. The apparatus employs an ellipsoidal furnace allowing for rapid heating and cooling. Using this apparatus nucleation and crystallization kinetic data was obtained leading to the construction of time-temperature-transformation curves for ZBLAN in microgravity and unit gravity.

Tucker, Dennis S.↗

NASA NTRS2022

Effect of Sulfur on siderophile element partitioning between olivine and martian mantle primary melt

Ni and Co variations in primary martian magmas exhibit anomalous incompatible behavior, which has remained an unexplained conundrum. Because martian magmas are S-rich, and some trace metals are reported to have enhanced solubility in S-bearing magmas, we have carried out a series of experiments to evaluate the effect of high-S melts on the olivine/melt partitioning of Ni, Co, Mn, V, and Cr. Near-liquidus experiments on a synthetic primary martian mantle melt (Yamato-980459 [Y98]) were completed in a piston-cylinder apparatus at 0.75 GPa. Previous studies in S-free systems illustrate that the partition coefficients for these elements are dependent chiefly on D(Mg(Ol/melt)) (the partition coefficient defined as wt% Mg in olivine/wt% Mg in melt, a proxy for temperature), and were used to calibrate a predictive expression that includes the effects of temperature [i.e., D(Mg(Ol/melt))], melt composition, and oxygen fugacity. These predictive expressions are then used to isolate any effect in DM olivine/melt due to dissolved sulfur. The results show that S might have a small effect for Co, but not enough to change Co partitioning from compatible to incompatible in our experiments. The addition of a sulfur term to the D(Co) predictive expressions shows that nearly 8000 ppm of sulfur would be required in the melt (at liquidus temperature of Y98) for D(Co) to become <1. These S contents are two times higher than those of a sulfide-saturated melt at the P-T conditions of a martian mantle source region. Therefore, the anomalous incompatible behavior observed in these primary magma suites must be due to another mechanism. High temperature, oxygen fugacity, and diffusion are not viable mechanisms, but magma mixing, assimilation, or kinetic crystallization effects remain possibilities.

shergottite↗

NASA NTRS1978

Effects of kinetics on the crystallization of quartz normative basalt 15597 - An experimental study

Equilibrium experiments on a residual liquid composition from the dynamic crystallization study on quartz normative basalt (QNB) 15597 are used to evaluate the effects of kinetics on the crystallization of pyroxene-porphyritic basalts. The results indicate that the liquids coexisting with pyroxene phenocryst rims before the precipitation of groundmass plagioclase + pyroxene have left the equilibrium liquid line of descent and metastably penetrated the plagioclase primary phase volume. The precipitation of groundmass plagioclase + pyroxene brings the basalt system closer to equilibrium with respect to the residual liquid and crystals. At rapid cooling rates pyroxene phenocryst growth produces substantial compositional gradients in the residual silicate liquid at the pyroxene/liquid interface. The compositional gradients enhance the nucleation and growth of groundmass phases at the phenocryst interface, because effects related to constitutional supercooling for these phases (e.g., plagioclase, pyroxene, etc.) favor nucleation at the interface.

Grove, T. L.↗

NASA NTRS2006

Determining Kinetic Parameters for Isothermal Crystallization of Glasses

Non-isothermal crystallization techniques are frequently used to determine the kinetic parameters for crystallization in glasses. These techniques are experimentally simple and quick compared to the isothermal techniques. However, the analytical models used for non-isothermal data analysis, originally developed for describing isothermal transformation kinetics, are fundamentally flawed. The present paper describes a technique for determining the kinetic parameters for isothermal crystallization in glasses, which eliminates most of the common problems that generally make the studies of isothermal crystallization laborious and time consuming. In this technique, the volume fraction of glass that is crystallized as a function of time during an isothermal hold was determined using differential thermal analysis (DTA). The crystallization parameters for the lithium-disilicate (Li2O.2SiO2) model glass were first determined and compared to the same parameters determined by other techniques to establish the accuracy and usefulness of the present technique. This technique was then used to describe the crystallization kinetics of a complex Ca-Sr-Zn-silicate glass developed for sealing solid oxide fuel cells.

Ray, C. S.↗