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An experimental investigation has obtained results indicating that neither LaF3 nor LiYF4 are acceptable alternatives to MgF2 as coatings for vacuum-deposited aluminum mirrors from which high UV reflectance down to 1150 A is required. Nevertheless, LaF3 may prove useful in those specialized applications in which the suppression of lower wavelength emissions, such as the 1216-A hydrogen line, is desirable.
The kinetics of crystallization of a number of fluorozirconate glasses were studied using isothermal and dynamic differential scanning calorimetry and X-ray diffraction. The addition of the fluorides LiF, NaF, AlF3, LaF3 to a base glass composition of ZrF4-BaF2 reduced the tendency to crystallize, probably by modifying the viscosity-temperature relation. ZrF4-BaF2-LaF3-AlF3-NaF glass was the most stable against devitrification and perhaps is the best composition for optical fibers with low scattering loss. Some glasses first crystallize out into metastable beta-BaZr2F10 and beta-BaZrF6 phases, which transform into the most stable alpha-phases when heated to higher temperatures. The size of the crystallites was estimated to be about 600 A from X-ray diffraction.
New advances in VUV thin film filter technology have been made using filter designs with multilayers of materials such as Al2O3, BaF2, CaF2, HfO2, LaF3, MgF2, and SiO2. Our immediate application for these filters will be in an imaging system to be flown on a satellite where a 2 X 9 R(sub E) orbit will expose the instrument to approximately 275 krads of radiation. In view of the fact that no previous studies have been made on potential radiation damage of these materials in the thin film format, we report on such an assessment here. Transmittances and reflectances of BaF2, CaF2, HfO2, LaF3, MgF2, and SiO2 thin films on MgF2 substrates, Al2O3 thin films on fused silica substrates, uncoated fused silica and MgF2, and four multilayer filters made from these materials were measured from 120 nm to 180 nm before and after irradiation by 250 krads from a Co-60 gamma radiation source. No radiation-induced losses in transmittance or reflectance occurred in this wavelength range. Additional postradiation measurements from 160 nm to 300 nm indicated a 3 - 5% radiation-induced absorption near 260 nm in some of the samples with MgF2 substrates. From these measurements it is concluded that far ultraviolet filters made from the materials tested should experience less that 5% change from exposure to up to 250 krads of high energy radiation in space applications.
A class of infrared detectors is proposed and experimental results are presented for a prototype device. The material used is LaF3, an ionic conductor with a capacitance that varies exponentially with temperature. The detectivity of a prototype detector is estimated from measured signal voltages and incident power, and a Johnson noise voltage calculated from the measured resistance. For the parameters characterizing this device the estimated detectivity is consistent with a theoretical prediction. The theory further predicts an optimum detectivity for much thinner devices than the prototypes.
The inventions and published papers related to the project are listed. The research with thin films of LaF3 deposited on GaAs substrates is reported along with improvements in photocapacitative MIS infrared detectors.
Improvement of the previously reported photocapacitive MIS infrared detectors has led to the development of exceptional room-temperature devices. Unoptimized peak detectivities on the order of 10 to the 13th cm sq rt Hz/W, a value which exceeds the best obtainable from existing solid-state detectors, have now been consistently obtained in Si and GaAs devices using high-capacitance LaF3 or composite LaF3/native-oxide insulating layers. The measured spectral response of representative samples is presented and discussed in detail together with a simple theory which accounts for the observed behavior. The response of an ideal MIS photocapacitor is also contrasted with that of both a conventional photoconductor and a p-i-n photodiode, and reasons for the superior performance of the MIS detectors are given. Finally, fundamental studies on the electrical, optical, and noise characteristics of the MIS structures are analyzed and discussed in the context of infrared-detector applications.
Damage in ZrF4-BaF2-LaF3 glass induced by high-energy electrons was studied by ESR and optical spectroscopy. An optical absorption band at 314 nm in the irradiated glass annealed rapidly above about 50 C, probably by a second-order reaction at room temperature; the ESR lines annealed very slowly at room temperature.
The production of heavy metal fluoride (HMF) glasses, and the effects of thermal treatments on the HMF glasses are investigated. ZrF4, BaF2, AlF3, LaF3, and NaF were utilized in the synthesis of zirconium-barium-lanthanum-aluminum-sodium fluoride glass. The purity of these starting materials, in particular ZrF4, is evaluated using XRD analysis. The data reveal that low temperature heating of ZrF4-H2O is effective in removing the water of hydration, but causes the production of ZrF4 and oxyfluorides; however, dehydration followed by sublimation results in the production of monoclinic ZrFe without water or oxyfluoride contaminants.
Both the transmittance and reflectance of 2 mm thick MgF2 substrates and of thin films of BaF2, CaF2, LaF3, MgF2, Al2O3, HfO2, and SiO2 deposited on these substrates were measured for the wavelength range 120 nm to 230 nm. Results for BaF2, LaF2 and MgF2 show promise as being good materials from which interference filters can be made. The software and related hardware needed to take large amounts of data automatically in future measurements of the transmittance and reflectance was developed.
Long quantum lifetimes reduce number of diodes required to pump. Pumping by laser diodes demonstrated with such common Nd laser materials as neodymium:yttrium aluminum garnet (Nd:YAG) and Nd:YLiF4, but such materials as Nd:LaF3, Nd:NaF.9YF3, and possibly Nd:YF3 more useful because of long lifetimes of their upper laser energy levels. Cost effectiveness primary advantage of solid-state laser materials having longer upper-laser-level lifetimes. Because cost of diodes outweighs cost of laser material by perhaps two orders of magnitude, cost reduced significantly.
The aim of this experiment was to test the optical behavior of 20 components and coatings subjected to space exposure. Most of them are commonly used for their reflective or transmittive properties in spaceborne optics. They consist in several kind of metallic and dielectric mirrors designed for the 0.12 to 10 microns spectrum, UV, and NIR bandpass filters, visible, and IR antireflecting coatings, visible/IR dichroic beam splitters, and visible beam splitter. The coatings were deposited on various substrates such as glasses, germanium, magnesium fluoride, quartz, zinc selenide, and kanigened aluminum. Several coating materials were used such as Al, Ag, Au, MgF2, LaF3, ThF3, ThF4, SiO2, TiO2, ZrO2, Al2O3, MgO, Ge, and ZnSe. Five samples of each component were manufactured. Two flight samples were mounted in such a way that one was directly exposed to space and the other looking backwards. The same arrangement was used for the spare samples stored on ground in a box identical to the flight one and they were kept under vacuum during the LDEF mission. Finally, one set of reference components was stocked in a sealed box under a dry nitrogen atmosphere. By comparing the preflight and postflight optical performances of the five samples of each component, it is possible to detect the degradations due to the space exposure.
ZrF4-BaF2-LaF3-AIF3-NaF (ZBLAN) optical fiber was flown on board the NASA's KC-135 microgravity aircraft to determine the effects of microgravity on crystal growth in this material. Fiber samples were placed in evacuated quartz ampoules and heated to the crystallization temperature in 0g, 1g, and 2g. The 1g and 2g samples were observed to slump and crystallize. The 0g samples showed no evidence of crystallization.
One of the greatest obstacles with the fluorozirconate ZBLAN (ZrF4-BaF2-LaF3-AIF3-NaF) is the problem of devitrification. Fluoride glasses have a narrow working range and the viscosity is a strong function of temperature. Rates of nucleation and growth of crystals in the glass depend on the viscosity, making these glasses unstable and prone to crystallization. The viscosity of ZBLAN at the drawing temperature is low, usually between two to five poise, so it is difficult to obtain fibers from their preform melts without crystallization. The preforms usually contain heterogeneous nuclei which grow into microcrystallites above the glass transition temperature, T(g). Since microcrystallites in an optical fiber cause extrinsic light scattering losses of the optical signal, fiber drawing must be completed in a short time to minimize the generation of light scattering centers. To keep these losses to a minimum and to fabricate low scattering loss fibers and other optical components, this research deals with the possibility of minimizing crystallite formation by removing the gravitational influence of solutal segregation of the ZBLAN elements. This report reviews the early work on the KC-135 aircraft, the development of the ZBLAN Rocket Experiment, preparations at the White Sands Missile Range, analysis of the flight and ground test results, lessons learned and future experimentation.
ZBLAN (ZrF4-BaF2-LaF3-AlF3-NaF) optical fibers were flown on NASA's reduced gravity KC135 aircraft and Conquest I sub-orbital rocket. The purpose of these experiments was to determine the effects of gravity on the crystallization process of this material. Fiber samples encapsulated in evacuated quartz ampoules were heated to the crystallization temperature during flight in reduced gravity and on the ground in unit gravity. Scanning electron and transmission electron microscopy were utilized to study the crystallization behavior. Samples heated under unit gravity conditions exhibited significant crystallization, while fibers heated to the crystallization temperature in reduced gravity showed no signs of crystallization. A mechanism based on microcellular convection is proposed to explain these observed behaviors.
International Space Station Alpha (ISSA) will provide a platform not only for materials research but also a possible means to produce products in space which cannot be easily produced on the ground. Some products may even be superior to those now produced in unit gravity due to the lack of gravity induced convection effects. Our research with ZrF4-BaF2-LaF3-AlF3-NaF (ZBLAN glass) has shown that gravity does indeed play a major role in the crystallization behavior of this material. At the present time ZBLAN is being produced on earth in fiber optic form for use in surgical lasers and fiber optic lasers among other applications. High attenuation coefficients, however, have kept this material from being used in other applications such as long haul data transmission links. The high attenuation coefficients are due to impurities which can be removed through improved processing techniques and crystals which can only be removed or prevented from forming by processing in a reduced gravity environment.
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.
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.
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.