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Paley, M. S.

Publications and source records attributed to Paley, M. S..

17 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2016

Mars Atmospheric In Situ Resource Utilization Projects at the Kennedy Space Center

The atmosphere of Mars, which is approximately 95% carbon dioxide (CO2), is a rich resource for the human exploration of the red planet, primarily by the production of rocket propellants and oxygen for life support. Three recent projects led by NASA's Kennedy Space Center have been investigating the processing of CO2. The first project successfully demonstrated the Mars Atmospheric Processing Module (APM), which freezes CO2 with cryocoolers and combines sublimated CO2 with hydrogen to make methane and water. The second project absorbs CO2 with Ionic Liquids and electrolyzes it with water to make methane and oxygen, but with limited success so far. A third project plans to recover up to 100% of the oxygen in spacecraft respiratory CO2. A combination of the Reverse Water Gas Shift reaction and the Boudouard reaction eventually fill the reactor up with carbon, stopping the process. A system to continuously remove and collect carbon is under construction.

in situ resource utilization↗
NASA NTRS2012

Task-Specific Ionic Liquids for Mars Exploration (Green Chemistry for a Red Planet)

Ionic Liquids (ILs) are organic salts with low melting points that are liquid at or near room temperature. The combinations of available ions and task-specific molecular designability make them suitable for a huge variety of tasks. Because of their low flammability, low vapor pressure, and stability in harsh environments (extreme temperatures, hard vacuum) they are generally much safer and "greener" than conventional chemicals and are thus suitable for a wide range of applications that support NASA exploration goals. This presentation describes several of the ongoing applications that are being developed at MSFC.

Karr, L. J.↗
NASA NTRS2001

All-Optical Logic Gates in Organic Materials

A picosecond switch made of polydiacetylene thin film coated on the interior of a 50-micron diameter hollow fiber and a nanosecond switch made of a micron thick film of phthalocyanine on glass were developed.

Adbeldayem, H. A.↗
NASA NTRS2001

Polydiacetylene as an all-optical picosecond Switch

Polydiacetylene derivative of 2-methyl-4-nitroaniline (PDAMNA) shows a picosecond switching property, which illustrated a partial all-optical picosecond NAND logic gate. The switching phenomenon was demonstrated by waveguiding two collinear beams at 633 nm and 532 nm through a hollow fiber of 50 micrometers diameter, coated from inside with a thin film of PDAMNA. A Z-scan investigations of a PDAMNA thin film on quartz substrate revealed that the switching effect was attributed to an excited state absorption in the systems. The studies also showed that the polymer suffers a photo-oxidation beyond an intensity level of 2.9 x 10(exp 6) w/square cm. The photo-oxidized film has different physical properties that are different from the original film before oxidation. The life time of both excited states before and after oxidation as well as their absorption coefficients were estimated by fitting a three level system model to the experimental results.

Abdeldayem, Hossin A.↗
NASA NTRS1998

Microgravity Processing and Photonic Applications of Organic and Polymeric Materials

In recent years, a great deal of interest has been directed toward the use of organic materials in the development of high-efficiency optoelectronic and photonic devices. There is a myriad of possibilities among organic which allow flexibility in the design of unique structures with a variety of functional groups. The use of nonlinear optical (NLO) organic materials such as thin-film waveguides allows full exploitation of their desirable qualities by permitting long interaction lengths and large susceptibilities allowing modest power input. There are several methods in use to prepare thin films, such as Langmuir-Blodgett (LB) and self-assembly techniques, vapor deposition, growth from sheared solution or melt, and melt growth between glass plates. Organics have many features that make Abstract: them desirable for use in optical devices such as high second- and third-order nonlinearities, flexibility of molecular design, and damage resistance to optical radiation. However, their use in devices has been hindered by processing difficulties for crystals and thin films. In this chapter, we discuss photonic and optoelectronic applications of a few organic materials and the potential role of microgravity on processing these materials. It is of interest to note how materials with second- and third-order nonlinear optical behavior may be improved in a diffusion-limited environment and ways in which convection may be detrimental to these materials. We focus our discussion on third-order materials for all-optical switching, and second-order materials for all-optical switching, and second-order materials for frequency conversion and electrooptics.

Frazier, Donald 0↗
NASA NTRS1998

The Effects of Ground and Space Processing on the Properties of Organic, Polymeric, and Colloidal Materials

In recent years, a great deal of interest has been directed toward the use of organic materials in the development of high-efficiency optoelectronic and phototonic devices. There is a myriad of possibilities among organic materials which allow flexibility in the design of unique structures with a variety of functional groups. The use of nonlinear optical (NLO) organic materials as thin film wave-guides allows full exploitation of their desirable qualifies by permitting long interaction lengths and large susceptibilities allowing modest power input. There are several methods in use to prepare thin films such as Langmuir-Blodgett (LB) and self-assembly techniques, vapor deposition, growth from sheared solution or melt, and melt growth between glass plates. Organic-based materials have many features that make them desirable for use in optical devices, such as high second-and third-order nonlinearity, flexibility of molecular design, and damage resistance to optical radiation. However, their use in devices has been hindered by processing difficulties for crystals and thin films. We discuss the potential role of microgravity processing of a few organic and polymeric materials. It is of interest to note how materials with second-and third-order NLO behavior may be improved in a diffusion-limited environment and ways in which convection may be detrimental to these materials. We focus our discussion on third-order materials for all-optical switching, and second-order materials for frequency conversion and electrooptics. The goal of minimizing optical loss obviously depends on processing methods. For solution-based processes, such as solution crystal growth and solution photopolymerization, it is well known that thermal and solutal density gradients can initiate buoyancy-driven convection. Resultant fluid flows can affect transport of material to and from growth interfaces and become manifest in the morphology and homogeneity of the growing film or crystal. Likewise, buoyancy-driven convection can hinder production of defect-free, high-quality crystals or films during crystal and film growth by vapor deposition.

Frazier, Donald O.↗
NASA NTRS1997

Effects of Convection During the Photodeposition of Polydiacetylene Thin Films

In this work, we describe a preliminary investigation of buoyancy-driven heat transfer during the growth of thin films from solution following exposure to ultraviolet (UV) light. Irradiation of the growth cell occurs at various directions relative to gravitational acceleration. Through numerical computations, the steady-state flow and temperature profiles are simulated during the course of light exposure. Light-induced polymerization accompanies a heat transfer process through a fairly complicated recirculating flow pattern. A scaling analysis shows that buoyancy-driven velocities only reduce by a factor of 10 for gravity levels as low as 10(exp -2)g(sub 0). Paley et al. observe what appears to be gravitationally sensitive particle development and inclusion in thin films using a photodeposition process. From this study it is clear that production of homogeneous thin films would have to occur in the environment of a complicated flow pattern of recirculation with a nonuniform temperature distribution. Indeed, even when irradiation occurs from the top of the cell, the most stable stratified cell orientation, defects remain in our films due to the persistence of buoyancy-driven convection. To achieve homogeneity, minimal scattering centers, and possible molecular order, photodeposition of polymer films by UV light exposure must proceed in a reduced-convection environment. Fluid mechanics simulations are useful for establishing gravitational sensitivity to this recently discovered process (patent # 5,451,433) for preparing thin films having quite promising nonlinear optical characteristics.

Frazier, D. O.↗
NASA NTRS1997

Effects of Convection during the Photodeposition of Polydiacetylene Thin Films

In this work, we describe a preliminary investigation of buoyancy-driven heat transfer during the growth of thin films from solution following exposure to ultraviolet (UV) light. Irradiation of the growth cell occurs at various directions relative to gravitational acceleration. Through numerical computations, the steady-state flow and temperature profiles are simulated during the course of light exposure. Light-induced polymerization accompanies a heat transfer process through a fairly complicated recirculating flow pattern. A scaling analysis shows that buoyancy-driven velocities only reduce by a factor of 10 for gravity levels as low as 10(exp -2) g(sub 0). Paley et al. observe what appears to be gravitationally sensitive particle development and inclusion in thin films using a photodeposition process. From this study, it is clear that production of homogeneous thin films would have to occur in the environment of a complicated flow pattern of recirculation with a nonuniform temperature distribution. Indeed, even when irradiation occurs from the top of the cell, the most stable stratified cell orientation, defects remain in our films due to the persistence of buoyancy-driven convection. To achieve homogeneity, minimal scattering centers, and possible molecular order, photodeposition of polymer films by UV light exposure must proceed in a reduced-convection environment. Fluid mechanics simulations are useful for establishing gravitational sensitivity to this recently discovered process (patent # 5,451,433) for preparing thin films having quite promising nonlinear optical characteristics.

Frazier, D. O.↗
NASA NTRS1996

Buoyancy-Driven Heat Transfer During Application of a Thermal Gradient for the Study of Vapor Deposition at Low Pressure Using and Ideal Gas

A mathematical model has been developed to determine heat transfer during vapor deposition of source materials under a variety of orientations relative to gravitational accelerations. The model demonstrates that convection can occur at total pressures as low as 10-2 mm Hg. Through numerical computation, using physical material parameters of air, a series of time steps demonstrates the development of flow and temperature profiles during the course of vapor deposition. These computations show that in unit gravity vapor deposition occurs by transport through a fairly complicated circulating flow pattern when applying heat to the bottom of the vessel with parallel orientation with respect to the gravity vector. The model material parameters for air predict the effect of kinematic viscosity to be of the same order as thermal diffusivity, which is the case for Prandtl number approx. 1 fluids. Qualitative agreement between experiment and the model indicates that 6-(2-methyl-4-nitroanilino)-2,4-hexadiyn-l-ol (DAMNA) at these pressures indeed approximates an ideal gas at the experiment temperatures, and may validate the use of air physical constants. It is apparent that complicated nonuniform temperature distribution in the vapor could dramatically affect the homogeneity, orientation, and quality of deposited films. The experimental test i's a qualitative comparison of film thickness using ultraviolet-visible spectroscopy on films generated in appropriately oriented vapor deposition cells. In the case where heating of the reaction vessel occurs from the top, deposition of vapor does not normally occur by convection due to a stable stratified medium. When vapor deposition occurs in vessels heated at the bottom, but oriented relative to the gravity vector between these two extremes, horizontal thermal gradients induce a complex flow pattern. In the plane parallel to the tilt axis, the flow pattern is symmetrical and opposite in direction from that where the vessel is positioned vertically. The ground-based experiments are sufficient preliminary tests of theory and should be of significant interest regarding vapor deposited films in microgravity.

Frazier, D. O.↗
NASA NTRS1996

Kinetic Studies on Photodeposition of Polydiacetylene Thin Film from Solution: Preliminary Determination of the Rate Law

Preliminary kinetic studies were undertaken on the photodeposition of thin films of a polydiacetylene derivative of 2-methyl-4-nitroaniline from monomer solutions onto quartz substrates. Solutions of the monomer, DAMNA, in 1,2-dichloroethane at various concentrations were irradiated at 364 nm using an argon-ion laser at several intensities. It was found that the rate of polydiacetylene (PDAMNA) film photodeposition varies linearly with UV light intensity and as the square root of monomer concentration.

Paley, M. S.↗
NASA NTRS1995

Photodeposition of amorphous polydiacetylene films from monomer solutions onto transparent substrates

Polydiacetylenes are a very promising class of polymers for both photonic and electronic applications because of their highly conjugated structures. For these applications, high-quality thin polydiacetylene films are required. We have discovered a novel technique for obtaining such films of a polydiacetylene derivative of 2-methyl-4-nitroaniline using photodeposition from monomer solutions onto UV transparent substrates. This heretofore unreported process yields amorphous polydiacetylene films with thicknesses on the order of I micron that have optical quality superior to that of films grown by standard crystal growth techniques. Furthermore, these films exhibit good third-order nonlinear optical susceptibilities; degenerate four-wave mixing experiments give x(3) values on the order of 10(exp -8) - 10(exp -7) esu. We have conducted masking experiments which demonstrate that photodeposition occurs only where the substrate is directly irradiated, clearly indicating that the reaction occurs at the surface. Additionally, we have also been able to carry out photodeposition using lasers to form thin polymer circuits. In this work, we discuss the photodeposition of polydiacetylene thin films from solution, perform chemical characterization of these films, investigate the role of the substrate, speculate on the mechanism of the reaction, and make a preliminary determination of the third-order optical nonlinearity of the films. This simple, straightforward technique may ultimately make feasible the production of polydiacetylene thin films for technological applications.

Paley, M. S.↗
NASA NTRS1994

Photodeposition of Thin Polydiacetylene Films from Solution that Exhibit Large Third-Order Optical Nonlinearities

One promising class of organic compounds for applications in the field of nonlinear optics (NLO) are polydiacetylenes, which are of interest because they are highly conjugated polymers capable of exhibiting very large optical nonlinearities with fast response times. During the course of crystal growth studies in anticipation of a space experiment, we discovered a novel, simple method for the formation of polydiacetylene thin films by photodeposition from monomer solutions onto quartz or glass substrates. Characterization of these PDAMNA films is not trivial; they are not soluble in common organic solvents, which makes the standard solution-based methods of polymer analysis useless.

Paley, M. S.↗
NASA NTRS1993

Diacetylene and Polydiacetylene Derivatives of 2-Methyl-4-Nitroaniline for Second-Harmonic Generation

A novel diacetylene derivative of 2-Methyl-4-NitroAniline (MNA), a well-known material for Second-Harmonic Generation (SHG), is synthesized. This monomer DiAcetylene MethylNitroAniline, (DAMNA) is characterized by means of the Kurtz technique at 1064 nm and is found to have an SHG powder efficiency 62.5 % that of MNA itself. Thin crystalline films of DAMNA are grown onto quartz, Teflon, and Kapton substrates by means of vapor deposition in vacuum. These films are then polymerized in the solid state by exposure to long-wavelength UV radiation to give crystalline polydiacetylene thin films (PDAMNA). The films are next characterized for SHG, using an unpolymerized DAMNA film as a reference. Interestingly, films grown onto Teflon exhibit greater orientation and significantly greater SHG than those grown onto quartz and Kapton. This result is promising in that it demonstrates the potential of PDAMNA as both a crystalline and polymeric material for SHG applications, in which highly oriented thin films are desired. Computational modeling (usingAM1) is also carried out on DAMNA and is compared to the experimental results.

Paley, M. S.↗
NASA NTRS1992

Synthesis, vapor growth, polymerization, and characterization of thin films of novel diacetylene derivatives of pyrrole. The use of computer modeling to predict chemical and optical properties of these diacetylenes and poly(diacetylenes)

In the present work two diacetylene derivatives of pyrrole which are predicted by semiempirical AM1 calculations to have very different properties, are synthesized; the polymerizability of these diacetylenes in the solid state is determined, and the results are compared to the computer predictions. Diacetylene 1 is novel in that the monomer is a liquid at room temperature; this may allow for the possibility of polymerization in the liquid state as well as the solid state. Thin poly(diacetylene) films are obtained from compound 1 by growing films of the monomer using vapor deposition and polymerizing with UV light; these films are then characterized. Interestingly, while the poly(diacetylene) from 1 does not possess good nonlinear optical properties, the monomer exhibits very good third-order effects (phase conjugation) in solution. Dilute acetone solutions of the monomer 1 give intensity-dependent refractive indices on the order of 10 exp -6 esu; these are 10 exp 6 times better than for CS2.

Paley, M. S.↗
NASA NTRS1991

Growth of thin films of organic nonlinear optical materials by vapor growth processes - An overview and examination of shortfalls

Research on the growth of second- and third-order nonlinear optical (NLO) organic thin film by vapor deposition is reviewed. Particular attention is given to the experimental methods for growing thin films of p-chlorophenylurea, diacetylenes, and phthalocyanines; characteristics of the resulting films; and approaches for advancing thin film technology. It is concluded that the growth of NLO thin films by vapor processes is a promising method for the fabrication of planar waveguides for nonlinear optical devices. Two innovative approaches are proposed including a method of controlling the input beam frequency to maximize nonlinear effects in thin films and single crystals, and the alternate approach to the molecular design of organic NLO materials by increasing the transition dipole moment between ground and excited states of the molecule.

Frazier, D. O.↗