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31 records · Page 2

Mechanisms for the Crystallization of ZBLAN

The objective of this ground based study is to test the hypothesis that shear thinning (the non-Newtonian response of viscosity to shear rate) is a viable mechanism to explain the observation of enhanced glass formation in numerous low-g experiments. In 1-g, fluid motion results from buoyancy forces and surface tension driven convection. This fluid flow will introduce shear in undercooled liquids in 1-g. In low-g it is known that fluid flows are greatly reduced so that the shear rate in fluids can be extremely low. It is believed that some fluids may have weak structure in the absence of flow. Very small shear rates could cause this structure to collapse in response to shear resulting in a lowering of the viscosity of the fluid. The hypothesis of this research is that: Shear thinning in undercooled liquids decreases the viscosity, increasing the rate of nucleation and crystallization of glass forming melts. Shear in the melt can be reduced in low-g, thus enhancing undercooling and glass formation. The viscosity of a model glass (lithium di-silicate, L2S) often used for crystallization studies has been measured at very low shear rates using a dynamic mechanical thermal analyzer. Our results are consistent with increasing viscosity with a lowering of shear rates. The viscosity of L2S may vary as much as an order of magnitude depending on the shear rate in the temperature region of maximum nucleation and crystal growth. Classical equations for nucleation and crystal growth rates, are inversely related to the viscosity and viscosity to the third power respectively. An order of magnitude variation in viscosity (with shear) at a given temperature would have dramatic effects on glass crystallization Crystallization studies with the heavy metal fluoride glass ZBLAN (ZrF2-BaF2-LaF3-AlF3-NaF) to examine the effect of shear on crystallization are being initiated. Samples are to be melted and quenched under quiescent conditions at different shear rates to determine the effect on crystallization. The results from this study are expected to advance the current scientific understanding of glass formation in low-g and glass crystallization under glass molding conditions and will improve the scientific understanding of technological processes such as fiber pulling, bulk amorphous alloys, and glass fabrication processes.

Ethridge, Edwin C.↗

Effects of Gravity on ZBLAN Glass Crystallization

The effects of gravity on the crystallization of ZrF4-BaF2-LaF3-AlF3- NaF glasses have been studied utilizing NASA's KC135 and a sounding rocket, Fibers and cylinders of ZBLAN glass were heated to the crystallization temperature in unit and reduced gravity. When processed in unit gravity the glass crystallized, but when processed in reduced gravity, crystallization was suppressed. A possible explanation involving shear thinning is presented to explain these results.

Tucker, Dennis S.↗

The Effects of Gravity on the Crystallization Behavior of Heavy Metal Fluoride Glasses

Heavy metal fluoride glasses are used in such applications as fiber lasers and laser amplifiers. ZrF4-BaF2-LaF3-AlF3-NaF (ZBLAN) is one of the more commonly used heavy metal fluoride glasses. ZBLAN is an infrared transmitter and has a theoretical attenuation coefficient of 0.002 db/km. However, due to impurities and small crystallites this attenuation coefficient has not been achieved to date. ZBLAN is a fragile glass which can lead to rapid crystallization, if the glass is not cooled rapidly to below the glass transition temperature or if the glass is reheated near the crystallization temperature for any period of time. Studies carried on at Marshall Space Flight Center and the University of Alabama in Huntsville since 1993 have shown that heating ZBLAN glass at the crystallization temperature in reduced gravity results in a suppression of crystallization when compared to ZBLAN processed in unit gravity. These studies utilized NASA's KC-135 aircraft and the Conquest sounding rocket. In the first series of experiments, short lengths of ZBLAN fiber were heated to the crystallization temperature in reduced gravity on board the KC- 135 and the Conquest sounding rocket and compared with fibers heated in unit gravity. The fibers processed in reduced gravity showed no evidence of crystallization when studied with x-ray diffraction and scanning electron microscopy. However, the fibers processed in unit gravity were completely crystallized. Subsequent experiments included heating small pieces of ZBLAN glass at the crystallization temperature while viewing with a video camera to follow the crystallization phenomenon. In this experiment crystallization was observed in reduced gravity, however, it was suppressed when compared to heating in unit gravity. In the most recent experiment on board the KC-135, rapid thermal analysis of ZBLAN was performed. A mechanism to explain the observations has been proposed. This mechanism is based on shear thinning whereby, the glass undergoes a reduction in viscosity in the 10(exp 5) - 10(exp 7) poise range, allowing more rapid diffusion and thus crystallization. It is proposed that this mechanism is suppressed in reduced gravity. An experiment is presently being conducted to test this theory. With increased knowledge of ZBLAN behavior in reduced gravity, three low earth orbit tiber drawing facilities have been designed. One would be suitable for use on the International Space Station, another while aboard the Space Shuttle and the third system is a fully automated facility which would operate independently of the ISS or Shuttle in a free float mode. The primary benefits of free floating a facility in LEO includes a higher quality of microgravity and reduced safety concerns since it is not in a manned environment.

Tucker, Dennis S.↗

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.↗

The Effects of a Magnetic Field on the Crystallization of a Fluorozirconate Glass

An axial magnetic field of 0.1T was applied to ZrF4-BaF2-LaF3-AlF3-NaF (ZBLAN) fibers during heating to the glass crystallization temperature. Scanning electron microscopy and x-ray diffraction were used to identify crystal phases. It was shown that fibers exposed to the magnetic field did not crystallize while fibers not exposed to the field did crystallize. A hypothesis based on magnetic work was proposed to explain the results and tested by measuring the magnetic susceptibilities of the glass and crystal.

Tucker, Dennis S.↗

Improved Mirror Coatings for Use in the Lyman Ultraviolet to Enhance Astronomical Instrument Capabilities

This paper will describe efforts at developing broadband mirror coatings with high performance that will extend from infrared wavelengths down to the Far-Ultraviolet (FUV) spectral region. These mirror coatings would be realized by passivating the surface of freshly made aluminum coatings with XeF2 gas in order to form a thin AlF3 overcoat that will protect the aluminum from oxidation and, hence, realize the high-reflectance of this material down to its intrinsic cut-off wavelength of 90 nm. Improved reflective coatings for optics, particularly in the FUV region (90-120 nm), could yield dramatically more sensitive instruments and permit more instrument design freedom.

reflectance↗

E-Beam Generated Plasma Etching for Developing High-Reflectance Mirrors for Far-Ultraviolet Astronomical Instrument Applications

Astronomical space telescopes to study astrophysical phenomena from the far-ultraviolet (FUV) to the near infrared (NIR) will require mirror coatings with high reflectance over this entire spectral region. While coatings for the optical and NIR part of the spectrum are fairly well developed with proven performance, the FUV presents significant challenges. The U.S. Naval Research Laboratory (NRL) has developed a processing system based on an electron beam-generated plasma that provides for controlled fluorination and/or etching of surfaces with near monolayer precision and minimal changes to surface morphology. In this paper, we report recent results of samples treated in the NRL Large Area Plasma Processing System (LAPPS) where restoration of the high intrinsic reflectance in the FUV spectral range have been observed of aluminum (Al) mirrors protected with a magnesium di-fluoride (MgF2) overcoat. This paper will also extend these studies to other Al mirrors protected with aluminum tri-fluoride (AlF3) in order to realize the high intrinsic reflectance Al down to FUV wavelengths (100−200 nm), while still maintaining the high reflectance in the optical and NIR spectral regions. Laboratory test data and optical diagnostic techniques used to verify surface scattering and durability of selected coatings will be presented. Finally, we will discuss the scalability of the LAPPS etching process in order to realize these high-reflectivity coatings on mirror segments as large as those proposed for the Large Ultraviolet, Optical, and Infrared (LUVOIR) astronomical telescope system (1+meter class).

LUVOIR↗

Electrostatic Levitation of ZBLAN and Chalcogenide Glasses

Heavy Metal Fluoride Glasses have been studied for approximately 35 years. ZrF4-BaF BaF2-LaF3-AlF3-NaF (ZBLAN) showed the most promise as an optical fiber. It transmits IR out to approximately 5 microns. Applications: fiber amplifiers, lasers and nuclear radiation resistant links. Intrinsic and Extrinsic processes limit light propagation; Intrinsic: band gap absorption, Rayleigh scatter and multiphonon absorption; Extrinsic: impurities such as rare-earth ions and crystallite formation. Theoretical loss coefficient is 0.001 dB/km. This loss has not been achieved to date due to intrinsic and extrinsic processes. ZBLAN fibers obtained from Infrared Focal Systems, Inc. and Bell Laboratories. Fibers were stripped of coating and placed in evacuated quartz ampoules. These fibers were first flown on NASA’s KC135 Reduced Gravity Aircraft. KC135 produces approximately 25 sec. of reduced gravity per parabola. One week of flights led to approximately 200 total parabolas. Fibers were heated to the crystallization temperature during reduced gravity and compared to unit gravity for the same amount of time. Fibers were also flown on board the Conquest sub-orbital rocket. This flight gave approximately 6.5 minutes of reduced gravity.

Tucker, Dennis S.↗

Influence of evaporation rate and chamber pressure on the FUV reflectance and physical characteristics of aluminum films

Space telescopes for studying astrophysical phenomena from the far ultraviolet (FUV) to the near infrared (NIR) require durable mirror coatings with high and uniform reflectance over a very broad spectral region. While coatings for the optical and NIR region are well developed with proven performance, the FUV band presents significant challenges, particularly below 115 nm. Recent developments in physical vapor deposition (PVD) coating processes of aluminum mirrors that are protected with a metal-fluoride overcoat to prevent oxidation (such as LiF, MgF2, or AlF3) have improved reflectance in the FUV. While the emphasis in these studies has been placed on improving the deposition conditions of the metal-fluoride overcoats, less attention has been devoted to how deposition parameters (such as vacuum conditions or deposition rates) may affect the quality of the aluminum mirrors. This paper presents characterization of Al+MgF2 coupons made by flash evaporation of aluminum followed by resistive evaporation of MgF2. Samples were manufactured under a variety of processing conditions and the relationship between processing variables and mirror FUV reflectivity is analyzed. Performance characterization was based on the measured near-normal reflectance in the FUV (90-180 nm), and normal-incidence transmittance in the visible was done to analyze the possible presence of pinholes in the mirror. We demonstrated pinhole-free Al/MgF2 mirrors deposited at room temperature with a reflectivity of 0.91 at 122 nm wavelength. This reflectivity enhancement was achieved solely through parameter optimization.

Manuel A. Quijada↗

Influence of Evaporation Rate and Chamber Pressure on the FUV Reflectance and Physical Characteristics of Aluminum Films

Space telescopes for studying astrophysical phenomena from the far ultraviolet (FUV) to the near infrared (NIR) require durable mirror coatings with high and uniform reflectance over a very broad spectral region. While coatings for the optical and NIR region are well developed with proven performance, the FUV band presents significant challenges, particularly below 115 nm. Recent developments in physical vapor deposition (PVD) coating processes of aluminum mirrors that are protected with a metal-fluoride overcoat to prevent oxidation (such as LiF, MgF2, or AlF3) have improved reflectance in the FUV. While the emphasis in these studies has been placed on improving the deposition conditions of the metal-fluoride overcoats, less attention has been devoted to how deposition parameters (such as vacuum conditions or deposition rates) may affect the quality of the aluminum mirrors. This paper presents characterization of Al+MgF2 coupons made by flash evaporation of aluminum followed by resistive evaporation of MgF2. Samples were manufactured under a variety of processing conditions and the relationship between processing variables and mirror FUV reflectivity is analyzed. Performance characterization was based on the measured near-normal reflectance in the FUV (90-180 nm), and normal-incidence transmittance in the visible was done to analyze the possible presence of pinholes in the mirror. We demonstrated pinhole-free Al/MgF2 mirrors deposited at room temperature with a reflectivity of 0.91 at 122 nm wavelength. This reflectivity enhancement was achieved solely through parameter optimization.

FUV reflectance, aluminum, PVD, deposition rate, A↗

Cryolite Overcoated Aluminum Reflectors for Far-Ultraviolet Spectroscopy

Aluminum (Al) mirrors are conventionally protected with metal-fluoride coatings (e.g., MgF2, LiF, or AlF3) immediately after deposition to prevent oxidation and preserve its far-ultraviolet (FUV) spectral efficiency. However, the resulting FUV reflectance of the aluminum reflector is limited by the metal-fluoride overcoat film index of refraction, morphology, stoichiometry, and its absorption cut-off in the lower end of the FUV spectra. Cryolite (sodium hexafluoroaluminate, Na3AlF6) emerges as a potential candidate to preserve the aluminum FUV reflectance due to its relatively lower index of refraction in the visible to ultraviolet; therefore, allowing for the thin-film design of highly spectral efficient reflectors over a wide spectral range. We investigate the use of cryolite in aluminum reflector FUV coating design. The deposited aluminum reflector overcoated with cryolite will be examined in terms of spectral efficiency and environmental durability. The deposited cryolite overcoat will be evaluated in terms of optical constants and structural properties. Preliminary results have shown that the use of cryolite as an overcoat to protect aluminum would yield unprecedented results as an optimal Hydrogen Lyman-alpha (HLyα) spectral line reflector, with experimental reflectance values >96%.

optical coatings↗

Stabilized Lithium, Manganese-Rich Layered Cathode Materials Enabled by Integrating Co-Doping and Nanocoating

While lithium, manganese-rich (LMR) layered oxide cathode materials offer high energy density (>900 Wh kg –1 ) and low cost, LMR is susceptible to continuous capacity and voltage decay from the oxygen migration and side reaction with aqueous electrolyte at high voltage. Herein, the integration of Na/F co-doping (CD) and AlF 3 coating on LMR is achieved without the need of complex atomic layer deposition. Akin to pristine and CD samples, CD with 1 wt % AlF 3 (CD-1.0 wt %) shows excellent electrochemical performance with the capacity and voltage retentions of 93 and 91% after 150 cycles at 0.5C, respectively, and increased ionic conductivity. Spectroscopic analysis indicates that the coating mainly influences the Co distribution, where Co is enriched on the surface, and partial diffusion of Al 3+ ions toward the bulk, leading to a slight change of transition-metal (TM) valence states at the nanometer scale and the formation of a stable Li x (CoAl)O y phase. Post-cycling analysis reveals that CD-1.0 wt % can alleviate the formation of rock-salt structure and Mn dissolution. Besides, little to no metal segregation is detected for the cycled CD-1.0 wt % sample. This finding presents the first instance to apply co-doping and AlF 3 coating as a new strategy to enhance the structural homogeneity and takes another step toward their commercial viability.

25 ENERGY STORAGE↗

Environmental and Polarization Characterizations of E-Beam Plasma-Based AlF 3 -Passivated Aluminum Mirrors for Astronomical Telescopes

Astronomical space telescopes to study astrophysical phenomena from the far ultraviolet (FUV) to the near infrared (NIR) will require mirror coatings with high reflectance over this entire spectral region. While coatings for the optical and NIR part of the spectrum are fairly well developed with proven performance, the FUV range has presented significant challenges, particularly below 120nm. Recent developments in electron-beam (e-Beam) generated plasma treatment in a SF 6 environments has enabled the effective passivation of aluminum (Al) coatings for applications in the FUV, by native oxide removal and the formation of a AlF 3 passivation layer which could be tuned to any desired AlF 3 thickness. These results have been produced through a collaboration between the Goddard Space Flight Center (GSFC) and the Naval Research Laboratory (NRL). The passivation experiments have been carried out using the Large Area Plasma Processing System (LAPPS) at NRL using bare aluminum samples and provided by the coating group at GSFC. This novel procedure has demonstrated improved Al mirrors with state-of-the-art FUV reflectivity (e.g. R=91% at 121.6nm). In this paper, we will be reporting on environmental testing, micro-roughness, as well as polarization studies of these E-beam treated samples. These characterizations are being done in order to advance the Technology Readiness Level (TRL) for these Al+AlF 3 mirror coatings produced at LAPPS. The ultimate goal is to demonstrate the promise of using this coating technology to deliver reflectance performance plus stability and uniformity over a large area for a future IR/O/UV space telescope observatory.

FUV reflectance↗