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Processing of semicrystalline polymers

Our research group has been interested in the processing-structure-property relationships in semicrystalline polymers and blends for many years. In situ real time x ray scattering at elevated temperatures is being used to monitor the development of structure. An ongoing collaboration with Dr. Malcolm Capel at the Brookhaven National Synchrotron Light Source allows the performance of real time wide and small angle x ray scattering to study the phase transformations in semicrystalline polymers. The first part of my presentation will be about our recent use of x ray scattering to study blends of poly(ethylene terephthalate) with polyarylates. The purpose of the next portion of the presentation is to show how we may study effects of self-deformation of polymers during processing in the gravity environment, using real time x ray scattering. In this way, how processing stresses alter the microstructure of semicrystalline polymers was learned, and ultimately microgravity processing strategies that will result in more uniform morphology in these polymers is hoped to be developed.

Cebe, Peggy↗

The importance of properties in modeling

Casting and welding of superalloys, stainless steel and titanium alloys are processes which can be improved through modeling of heat flow, fluid flow, residual stress development, and microstructural evolution. These simulations require inputs of thermophysical data, some of which involves the partially or totally liquid state. In particular, these processes involve melting, flow in the liquid, and solidification. Modeling of such processes can lead to an improved understanding of defects such as shrinkage, inclusions, cracks, incomplete filling (or penetration), macrosegregation, improper grain structure, and deviations from dimensional specifications. Effective modeling can shorten process development time and improve quality. An approach to these problems is to develop efficient models; validate through correlations with thermal, distortion, and microstructural data; run parametric studies; extract knowledge based rules; and apply to adaptive closed loop control systems. With the appropriate pre- and post-processing, such analyses can be made 'user friendly'. This would include graphical user interfaces as well as realistic images and color maps. In such form, these models can be used for sensitivity analyses, which are useful in defining appropriate sensors and in the development of control strategies. Such modeling can be done at several levels, e.g., the MARO level, modeling large scale phenomena such as heat and fluid flow or material deformation; the MICRO level, modeling the development of dendrites, grains or precipitates; or at the NANO level, modeling point defects, dislocations, stacking faults, etc. There are many computational issues associated with these simulations, e.g. computational efficiency and accuracy. In addition, there are many materials issues, not the least of which is the availability of accurate high temperature thermophysical data for complex alloys. This would include latent heat of fusion, temperature dependent heat capacity and thermal conductivity (for liquid and solid), viscosity, surface tension, thermal expansion, mechanical properties, etc. Preliminary data is frequently gathered from the literature; however, this is often not available for modern alloys. If additional data are required, measurements can be used; however, these are costly, time consuming and can be erroneous due to a lack of testing standards or impure materials. Microstructural predictors can be extracted from thermal information, e.g. cooling rate and thermal gradient; the prediction of microstructure is dependent on solidus and liquidus temperature, mushy zone permeability, the solidification curve, volume changes, phase transformations, alloying effects (such as surface tension or viscosity), mold/metal reactions, metal/environment reactions, etc. Defect maps may be needed to predict the onset of shrinkage, hot cracking or 'freckling'. Constants may be needed for stress relaxation, dendrite coarsening, vaporization, etc. Visualization was used as a tool to better comprehend complex data sets associated with the analysis of directional solidification (including crystal growth) and welding. Examples include not only isotherms, but also cooling rate, growth rate and thermal gradient. The latter two are not single valued scalars, but rather time and space dependent vector fields. Efficient models were developed for both casting and welding to predict heat flow and the relationship to dendrite and grain growth. These codes include many of the non-linear effects, e.g. radiation, which dominate these processes. The home-built FDM code(s) were designed to be useful not only to the scientist, but also to the process engineer. Special output can be requested to compare directly to experimental data. Visualization procedures were developed to visualize critical results, e.g. fusion zone width at the surface opposite that where the arc is applied ('penetration'). Both elaborate and simplified distortion analyses were carried out. It is clear that extensive mechanical property data are critical in order to accurately predict residual stress patterns. A scheme is currently being developed to integrate these modeling tools into a set of control algorithms; however, the success of this approach is critically dependent on the availability of accurate high temperature thermophysical data.

Giamei, A. F.↗

Dynamic measurements of thermophysical properties of metals and alloys at high temperatures by subsecond pulse heating techniques

Rapid (subsecond) heating techniques developed at the National Institute of Standards and Technology for the measurements of selected thermophysical and related properties of metals and alloys at high temperatures (above 1000 C) are described. The techniques are based on rapid resistive self-heating of the specimen from room temperature to the desired high temperature in short times and measuring the relevant experimental quantities, such as electrical current through the specimen, voltage across the specimen, specimen temperature, length, etc., with appropriate time resolution. The first technique, referred to as the millisecond-resolution technique, is for measurements on solid metals and alloys in the temperature range 1000 C to the melting temperature of the specimen. It utilizes a heavy battery bank for the energy source, and the total heating time of the specimen is typically in the range of 100-1000 ms. Data are recorded digitally every 0.5 ms with a full-scale resolution of about one part in 8000. The properties that can be measured with this system are as follows: specific heat, enthalpy, thermal expansion, electrical resistivity, normal spectral emissivity, hemispherical total emissivity, temperature and energy of solid-solid phase transformations, and melting temperature (solidus). The second technique, referred to as the microsecond-resolution technique, is for measurements on liquid metals and alloys in the temperature range 1200 to 6000 C. It utilizes a capacitor bank for the energy source, and the total heating time of the specimen is typically in the range 50-500 micro-s. Data are recorded digitally every 0.5 micro-s with a full-scale resolution of about one part in 4000. The properties that can be measured with this system are: melting temperature (solidus and liquidus), heat of fusion, specific heat, enthalpy, and electrical resistivity. The third technique is for measurements of the surface tension of liquid metals and alloys at their melting temperature. It utilizes a modified millisecond-resolution heating system designed for use in a microgravity environment.

Cezairliyan, Ared↗

Calorimetric thermometry of meteoritic troilite: Preliminary thermometer relationships

Thermodynamic properties of the alpha/beta phase transformation in terrestrial troilite (FeS), as measured by differential scanning calorimetry (DSC), vary systematically with prior thermal history of the troilite, as imposed under laboratory conditions. Both the transition temperature and enthalpy change for the alpha/beta transformation decrease with increasing maximum temperature of prior heat treatment. DSC measurements on troilite from various meteorites indicate clear differences in the alpha/beta thermodynamic properties that are consistent with differences in the natural thermal histories of the meteorites.

Allton, Judith H.↗

Calorimetric thermobarometry of experimentally shocked quartz

Structural damage in experimentally shock-metamorphosed, granular quartz is quantitatively measurable by differential scanning calorimetry (DSC). Shock-induced loss of crystallinity is witnessed by disappearance of the alpha/beta phase transformation and evolution of a broad endoenthalpic strain peak at 650-900 K. The strain-energy peak grows rapidly at less than 10 GPa but declines with increasing shock pressure; it approaches zero at 32 GPa where vitrification is extensive. Effects of grain size and post-shock thermal history must be better understood before calorimetric thermobarometry of naturally shocked samples becomes possible.

Ocker, Katherine D.↗

Analytic modeling of soot nucleation under fuel rich conditions

The objective of the present research is to construct a soot nucleation model according to a proposed chemical kinetic scheme to delineate quantitatively the nucleation mechanism in the soot formation process. Instead of following the traditional views which generally associate sooting with the homogeneous nucleation process in phase transformation or polymerization, we choose a chemical kinetic approach. In our proposed scheme the number of carbon atoms in the intermediate species between the fuel molecule and soot nuclei is continuously increased by radical additions. The number of hydrogen atoms in the intermediate species on the other hand is steadily decreased by radical dehydrogenation. When the number of carbon atoms in each of the intermediate molecules has exceeded a certain limit and the number of hydrogen atoms has fallen below a certain level, they may coagulate with one and another to form a larger molecule which is regarded as the initial soot nuclei in the present theory. Further coagulation and surface growth of the nuclei will lead to observable soot particles.

Yang, C. H.↗

Superconductivity in Russia: Update and prospects

The research projects and new technological developments that have occured in Russia are highlighted in this document. Some of the research discussed includes: x-ray structure analysis of YBCO superconducting single crystals and accompanying phase transformations; the role of electron-electron interaction in High Temperature Superconductors (HTSC); the formation of Cooper pairs in crystals; the synthesis and research on a new family of superconductors based on complex copper and mercury oxides (HgBa2CuO4 + alpha and HgBa2CaCu2O6 + alpha); methods for the extraction of higher (up to C200) fullerenes and metalfullerenides has been developed; and process of production of Josephson junctions and development of SQUID's.

Ozhogin, V.↗

Improved Damage Resistant Composite Materials Incorporating Shape Memory Alloys

Metallic shape memory alloys (SMA) such as nitinol have unique shape recovery behavior and mechanical properties associated with a material phase change that have been used in a variety of sensing and actuation applications. Recent studies have shown that integrating nitinol-SMA actuators into composite materials increases the composite material's functionality. Hybrid composites of conventional graphite/epoxy or glass/epoxy and nitinol-SMA elements can perform functions in applications where monolithic composites perform inadequately. One such application is the use of hybrid composites to function both in load bearing and armor capacities. While monolithic composites with high strength-to-weight ratios function efficiently as loadbearing structures, because of their brittle nature, impact loading can cause significant catastrophic damage. Initial composite failure modes such as delamination and matrix cracking dissipate some impact energy, but when stress exceeds the composite's ultimate strength, fiber fracture and material perforation become dominant. One of the few methods that has been developed to reduce material perforation is hybridizing polymer matrix composites with tough kevlar or high modulus polyethynylene plies. The tough fibers increase the impact resistance and the stiffer and stronger graphite fibers carry the majority of the load. Similarly, by adding nitinol-SMA elements that absorb impact energy through the stress-induced martensitic phase transformation, the composites' impact perforation resistance can be greatly enhanced. The results of drop-weight and high velocity gas-gun impact testing of various composite materials will be presented. The results demonstrate that hybridizing composites with nitinol-SMA elements significantly increases perforation resistance compared to other traditional toughening elements. Inspection of the composite specimens at various stages of perforation by optical microscope illustrates the mechanisms by which perforation is initiated. Results suggest that the out-of-plane transverse shear properties of the composite and nitinol elements have a significant effect on the perforation resistance. Applications that can utilize the hybrid composites effectively will also be presented with the experimental studies.

Paine, Jeffrey S. N.↗

Numerical Model for Isothermal and Non-Isothermal Crystallization of Liquids and Glasses

A new numerical model of isothermal and non-isothermal first order phase transformations, such as the crystallization of liquids and glasses, is presented. This model computes directly the volume fraction transformed, taking into account time-dependent nucleation rates and cluster-size-dependent growth velocities. The model is applied to the crystallization of lithium disilicate glass, using the appropriate kinetic and thermodynamic parameters. The model is used (1) to determine the validity of common methods for computing the volume fraction transformed as a function of time in isothermal experiments when a time-dependent nucleation rate is expected, (2) to simulate non-isothermal differential scanning calorimetry (DSC) studies of glass devitrification as a function of scan rate, and (3) to compute the effect of preannealing on the DSC peak parameters. A novel behavior of the nucleation rate with scan rate is predicted, arising because the relaxation of the cluster distribution cannot be described by a single relaxation time. Comparisons of the calculations with experimental data on this glass demonstrate the validity of the model.

Kelton, K. F.↗

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.↗

Analysis and Modeling of a Two-Phase Jet Pump of a Thermal Management System for Aerospace Applications

Jet pumps are devices capable of pumping fluids to a higher pressure by inducing the motion of a secondary fluid employing a high speed primary fluid. The main components of a jet pump are a primary nozzle, secondary fluid injectors, a mixing chamber, a throat, and a diffuser. The work described in this paper models the flow of a two-phase primary fluid inducing a secondary liquid (saturated or subcooled) injected into the jet pump mixing chamber. The model is capable of accounting for phase transformations due to compression, expansion, and mixing. The model is also capable of incorporating the effects of the temperature and pressure dependency in the analysis. The approach adopted utilizes an isentropic constant pressure mixing in the mixing chamber and at times employs iterative techniques to determine the flow conditions in the different parts of the jet pump.

Sherif, S.A.↗

Development of Advanced Multizone Facilities for Microgravity Processing

NASA has been interested in experimental ground based study to investigate the fundamental processes involved in phase transformation processes during growth of metallic, nonmetallic and electronic materials. Solidification, vapor growth and solution growth techniques of growing crystals are of special interest because of the inherent importance of convection in the nutrient solution. Convection enhances the mass transport through the nutrient and results in faster growth rates. Availability of low gravity environment of space has provided scientists a new variable to control the extent of convection and thus isolate the diffusive phenomena for their better understanding. The thermal gradient at the liquid-solid interface is determined by the alloy characteristics, the hot zone temperature, cold zone temperature and the width of the insulating zone. The thermal profiles get established by the existing material and geometrical constraints of the experimental set up. The major effort under this research was devoted to designing a programmable furnace which can be used to obtain thermal profiles along the length of the sample as per the demands of the scientists. The furnace did not have active cooling of the zones. Only active heating and passive cooling were utilized.

Source record↗

Planetary Geophysics and Tectonics

Research supported by grant NAGW-1928 has addressed a variety of problems related to planetary evolution. One important focus has been on questions related to the role of chemical buoyancy in planetary evolution with application to both Venus and the Moon. We have developed a model for the evolution of the Moon (Hess and Parmentier, 1995) in which dense, highly radioactive, late stage magma ocean cumulates sink forming a core. This core heats the overlying, chemically layered mantle giving rise to a heated, chemically well-mixed layer that thickens with time. This Mixed layer eventually becomes hot enough and thick enough that its top begins to melt at a pressure low enough that melt is buoyant, thus creating mare basalts from a high pressure source of the correct composition and at an appropriate time in lunar evolution. In work completed during the last year, numerical experiments on convection in a chemically stably stratified fluid layer heated from below have been completed. These results show us how to calculate the evolution of a mixed layer in the Moon, depending on the heat production in the ilmenite- cumulate core and the chemical stratification of the overlying mantle. Chemical stratification of the mantle after its initial differentiation is would trap heat in the deep interior and prevent the rapid rise of plumes with accompanying volcanism. This trapping of heat in the interior can explain the thickness of the lunar lithosphere as a function of time as well as the magmatic evolution. We show that heat transported to the base of the lithosphere at a rate determined by current estimates of radioactivity in the Moon would not satisfy constraints on elastic lithosphere thickness from tectonic feature associated with basin loading. Trapping heat at depth by a chemically stratified mantle may also explain the absence of global compressional features on the surface that previous models predict for an initially hot lunar interior. For Venus, we developed a model in which the chemical buoyancy of crust and a depleted mantle layer stabilizes the lithosphere for long periods of time and provides a mechanism of episodic planetary evolution (Parmentier and Hess, 1992). Continued thickening of a residual depleted mantle layer eventually suppresses pressure release melting and the creation of depleted mantle. Continued cooling then allows the lithosphere to become heavier than the underlying hotter, undepleted mantle. This repeated instability can occur on time scales appropriate for episodic global resurfacing on Venus. We have also examined the role of the gabbro-eclogite phase transformation on crust and lithosphere stability and as a mechanism of crustal recycling in the absence of plate tectonics. Our work thus far concentrates on the scale of instability that would occur due to cooling or crustal thickening associated with horizontal shortening. Whether repeated overturn can explain the evolution of Venus depends in part on whether sufficient heat transfer can occur between overturns and on constraints provided by understanding observed surface features and evolution.

Parmentier, E. M.↗

Time Temperature-Precipitation Behavior in An Al-Cu-Li Alloy 2195

Al-Cu-Li alloy 2195, with its combination of good cryogenic properties, low density, and high modulus, has been selected by NASA to be the main structural alloy of the Super Light Weight Tank (SLWT) for the Space Shuttle. Alloy 2195 is strengthened by an aging treatment that precipitates a particular precipitate, labeled as T1(Al2CuLi). Other phases, such as GP zone, (theta)', (theta)", theta, (delta)', S' are also present in this alloy when artificially aged. Cryogenic strength and fracture toughness are critical to the -SLWT application, since the SLWT will house liquid oxygen and hydrogen. Motivation for the Time-Temperature-Precipitation (TTP) study at lower temperature (lower than 350 F) comes in part from a recent study by Chen, The study found that the cryogenic fracture toughness of alloy 2195 is greatly influenced by the phases present in the matrix and subgrain boundaries. Therefore, the understanding of TTP behavior can help develop a guideline to select appropriate heat treatment conditions for the desirable applications. The study of TTP behavior at higher temperature (400 to 1000 F) was prompted by the fact that the SLWT requires a welded construction. Heat conduction from the weld pool affects the microstructure in the heat-affected zone (HAZ), which leads to changes in the mechanical properties. Furthermore, the SLWT may need repair welding for more than one time and any additional thermal cycles will increase precipitate instability and promote phase transformation. As a result considerable changes in HAZ microstructure and mechanical properties are expected during the construction of the SLWT. Therefore, the TTP diagrams can serve to understand the thermal history of the alloy by analyzing the welded microstructure. In the case welding, the effects of thermal cycles on the microstructure and mechanical properties can be predicted with the aid of the TTP diagrams. The 2195 alloy (nominally Al + 4 pct Cu + 1 pct Li + 0.3 pct Ag + 0.3 pct Mg + 0.1 pct Zr) used in this study was received in the form of 1.7 inch thick rolled plates. In brief goal of this study is to develop TTR diagram for the solutiontreated and stretched alloy 2195 from which the precipitation sequence at any service or aging conditions can be preducted.A subgrain boundary TTR diagram is also presented since precipitations at subgrain boundary can control and/or modify a wide veriety of material properties, such as cryogenic fracture toughness.

Chen, P. S.↗

Current Experiments in Microgravity

The Materials Science program within NASA's Microgravity Research Division will be outlined. Particular emphasis will be placed on those experiments slated for the International Space Station which pertain to high temperature materials. These include experiments designed to examine theories pertaining to solidification and pattern selection, coarsening and phase transformation.

Gillies, Donald C.↗

The Structure of Ice Nanoclusters: Implications for Interstellar Ice Grains

Crystalline ice nanoclusters and thin-films of pure and impure water ice were deposited and studied in order to evaluate the extent to which surface-related effects control bulk properties. In pure water ice nanoclusters and thin-films of impure water ice, the cubic to hexagonal phase transformation occurs at lower temperatures than in thin-film deposits of pure water ice. In laboratory-grown crystalline ice nanoclusters, approx. 20 nm diameter, a significant proportion of water molecules exists in surface and near-surface environments which have an amorphous or nearly amorphous character. These disordered regions, which are highly reactive, serve to promote transformations or reactions which would otherwise be kinetically hindered. Likewise, dilute impurities such as methanol, sequestered to the surface of thin-films on crystallization, introduce defects into the ice network, thereby allowing sluggish structural transitions to proceed. These structural effects, which are surface phenomena, are believed to play an important role in promoting molecular reactions known to occur within interstellar ice grains in cold molecular clouds, where the first organic compounds are formed.

Delzeit, L.↗

The Structure of Ice Nanoclusters and Thin-films of Water Ice: Implications for Icy Grains in Cold Molecular Clouds

The cubic to hexagonal phase transformation in water ice (I(sub c) yields I(sub h)) is used to measure the extent to which surface structure and impurities control bulk properties. In pure crystalline (I(sub c)) water ice nanoclusters and in thin-films of impure water ice, I(sub c) yields I(sub h) occurs at lower temperatures than in thin-films of pure water ice. The disordered surface of the 20 nm diameter nanoclusters promotes transformations or reactions which would otherwise be kinetically hindered. Likewise, impurities such as methanol introduce defects into the ice network, thereby allowing sluggish structural transitions to proceed. Such surface-related phenomena play an important role in promoting chemical reactions on interstellar ice grains within cold molecular clouds, where the first organic compounds are formed.

Delzeit, Lance↗

Interfacial Surgery Determination of Succinonitrile and Succinonitrile-Acetone Alloy Using Surface Light Scattering Spectrometer

The objectives of this ground based research is to measure the liquid/vapor interfacial surface energies of succinonitrile (SCN) and alloys of succinonitrile and acetone using Surface Light Scattering Spectrometer. Liquid/vapor interfacial energy measurements will be made near and above the melting point and are the primary goal of this proposal. A measurement of viscosity also results from the Surface Light Scattering technique employed. Interfacial free energies between the phases enters into many analysis of phase transformation and flow, including nucleation, dendritic growth, interface stability, Ostwald ripening, and Marangoni flow. Succirionitrile (SCN) is useful as a model for the study of metal solidification, although it is an organic material, it has a BCC crystal structure and solidifies dendriticly like a metal. It is also transparent and has a low melting point (58.08 C). Succinonitrile has been and is being used extensively in NASAs Microgravity Materials Science and Fluid Physics programs and as well as in several ground-based and microgravity studies including the Isothermal Dendritic Growth Experiment (IDGE) due to Glicksman and coworkers and subsequently in several theoretical and numerical studies of dendritic growth. Previous measurements of succinonitrile (SCN) and alloys of succinonitrile and acetone surface tensions are extremely limited. We believe the data sought through this proposal have significant basic physical property data value and thus the work proposed will provide needed data in support of NASAs Microgravity program research.

Tin, Padetha↗