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Temperature fluctuations in the canonical ensemble

We report the first quantitative measurements of spontaneous temperature fluctuations in a physical system well modeled by a canonical ensemble. Using superconducting magnetometers and a carefully controlled thermal environment, we have measured the noise spectra of paramagnetic salt thermometers that were coupled to thermal reservoirs at 2 K. The noise spectra were found to be in very good agreement with the predictions of the fluctuation-dissipation theorem. Our observations are at variance with some interpretations of fluctuations in the canonical ensemble.

Chui, T. C. P.↗

Selected spectroscopic and magnetic properties of lanthanide complexes in polyimide XU-218

Polyimide XU-218 films containing approximately 5 wt pct of Eu(III), Gd(III), Tb(III), and Er(III) were prepared, and the effects of complexing each of the metals with the following four ligands were investigated: N-phenylphthalamate (NPPA), 2,4-pentanedionate (AcAc), 1,3-diphenyl 1,3-propanedionate (DBM), and a new hexa-aza-macrocyclic (MAC) ligand. The tris-chelated complexes of the mononegative ligands NPPA, AcAc, and DBM produced transparent, flexible films, which had magnetic and spectral properties very similar to those of the parent lanthanide complexes, while complexes of MAC showed problems due to the presence of lattice water and yielded dark brittle films. AcAc caused little or no effect on the glass transition temperature (Tg), while NPPA and DBM complexes lowered Tg to 269-290 C, and MAC indicated moisture by inflexion at 95-100 C with a true Tg at 320 C. All lanthanide-containing films were paramagnetic.

Stoakley, D. M.↗

The 0.1K bolometers cooled by adiabatic demagnetization

The most straightforward way of reducing the noise equivalent power of bolometers is to lower their operating temperature. We have been exploring the possibility of using conventionally constructed bolometers at ultra-low temperatures to achieve NEP's suitable to the background environment of cooled space telescopes. We have chosen the technique of adiabatic demagnetization of a paramagnetic salt as a gravity independent, compact, and low power way to achieve temperatures below pumped He-3 (0.3 K). The demagnetization cryostat we used was capable of reaching temperatures below 0.08 K using Chromium Potassium Alum as a salt from a starting temperature of 1.5 K and a starting magnetic field of 30,000 gauss. Computer control of the magnetic field decay allowed a temperature of 0.2 K to be maintained to within 0.5 mK over a time period exceeding 14 hours. The refrigerator duty cycle was over 90 percent at this temperature. The success of these tests has motivated us to construct a more compact portable adiabatic demagnetization cryostat capable of bolometer optical tests and use at the 5m Hale telescope at 1mm wavelengths.

Roellig, T.↗

High Resolution Transmission Electron Microscopy (HRTEM) of nanophase ferric oxides

Iron oxide minerals are the prime candidates for Fe(III) signatures in remotely sensed Martian surface spectra. Magnetic, Mossbauer, and reflectance spectroscopy have been carried out in the laboratory in order to understand the mineralogical nature of Martian analog ferric oxide minerals of submicron or nanometer size range. Out of the iron oxide minerals studied, nanometer sized ferric oxides are promising candidates for possible Martian spectral analogs. 'Nanophase ferric oxide (np-Ox)' is a generic term for ferric oxide/oxihydroxide particles having nanoscale (less than 10 nm) particle dimensions. Ferrihydrite, superparamagnetic particles of hematite, maghemite and goethite, and nanometer sized particles of inherently paramagnetic lepidocrocite are all examples of nanophase ferric oxides. np-Ox particles in general do not give X-ray diffraction (XRD) patterns with well defined peaks and would often be classified as X-ray amorphous. Therefore, different np-Oxs preparations should be characterized using a more sensitive technique e.g., high resolution transmission electron microscopy (HRTEM). The purpose of this study is to report the particle size, morphology and crystalline order, of five np-Ox samples by HRTEM imaging and electron diffraction (ED).

Golden, D. C.↗

Heat capacity and thermal relaxation of bulk helium very near the lambda point

In October 1992 a low temperature experiment was flown on the Space Shuttle in low Earth orbit. The objective of the mission was to measure the heat capacity and thermal conductivity of helium very close to the lambda point with the smearing effect of gravity removed. We report preliminary results from the experiment, and compare them with related measurements performed on the ground. The sample was s sphere of helium 3.5 cm in diameter contained within a copper calorimeter of vey high thermal conductivity. The calorimeter was attached to a pair of high resolution paramagnetic salt thermometers with noise levels in the 10(exp -10) K range and suspended from a high stability thermal isolation system. During the mission we found that the resolution of the thermometers was degraded somewhat due to the impact of charged particles. This effect limited the useful resolution of the measurements to about two nanokelvins from the lambda point. The results reported here are limited to about ten nanokelvins from the transition.

Lipa, John A.↗

Critical review of electrical conductivity measurements and charge distribution analysis of magnesium oxide

The electrical conductivity sigma of MgO single crystals shows a sharp increase at 500-800 C, in particular of sigma surface, generally attributed to surface contamination. Charge Distribution Analysis (CDA), a new technique providing information on fundamental properties that was previously unavailable, allows for the determination of surface charges, their sign and associated internal electric field. Data on 99.99% purity, arc-fusion grown MgO crystals show that mobile charge carriers start to appear in the bulk of the MgO crystals between 200 and 400 C when sigma (measured by conventional techniques) is in t he 10(exp -14) to 10(exp -16) /omega/cm range. Above 500 C, as sigma increases to 10(exp -6) to 10(exp -7)/omega/cm, more charges appear giving rise to a strong positive surface charge supported by a strong internal field. This indicates that charges are generated in the bulk and diffuse to the surface by an internally controlled process. On the basis of their positive sign they are identified as holes (defect electrons). Because of the low cation content of these very pure MgO crystals, theses holes cannnot be associated with transition metal impurties. Instead, they are associated with the O(2-) sublattice, e.g. consist of O(-) states or positive holes. This conclusion is supported by magnetic susceptibility data showing the appearance of 1000 +/- 500 ppm paramagnetic species between 200-500 C. The magnetic data are consistent with strongly coupled, diamagnetic O(-) pairs below 200-500 C, chemically equivalent to peroxy anions, O2(2-), and probably associated with cation vacancies in the MgO matrix. The formation of O2(2-) in arc-fusion grown MgO crystals is very unexpected because of the highly reducing growth conditions. Their presence implies an internal redox reaction involving dissolved 'water' by which OH(-) pairs convert to O2(2-) plus H2 molecules. This redox conversion is supported by mass spectroscopic measurements of the H2 release from highly OH(-)-doped, finely divided MgO and by wet-chemical analysis of its oxidant concentration.

Freund, Friedemann↗

Hematite, pyroxene, and phyllosilicates on Mars: Implications from oxidized impact melt rocks from Manicouagan Crater, Quebec, Canada

Visible and near-IR refectivity, Moessbauer, and X ray diffraction data were obtained on powders of impact melt rock from the Manicouagan Impact Crater located in Quebec, Canada. The iron mineralogy is dominated by pyroxene for the least oxidized samples and by hematite for the most oxidized samples. Phyllosilicate (smectite) contents up to approximately 15 wt % were found in some heavily oxidized samples. Nanophase hematite and/or paramagnetic ferric iron is observed in all samples. No hydrous ferric oxides (e.g., goethite, lepidocrocite, and ferrihydrite) were detected, which implies the alteration occurred above 250 C. Oxidative alteration is thought to have occurred predominantly during late-stage crystallization and subsolidus cooling of the impact melt by invasion of oxidizing vapors and/or solutions while the impact melt rocks were still hot. The near-IR band minimum correlated with the extent of aleration Fe(3+)/Fe(sub tot) and ranged from approximately 1000 nm (high-Ca pyroxene) to approximately 850 nm (bulk, well-crystalline hematite) for least and most oxidized samples, respectively. Intermediate band positions (900-920 nm) are attributed to low-Ca pyroxene and/or a composite band from hematite-pyroxene assemblages. Manicouagan data are consistent with previous assignments of hematite and pyroxene to the approximately 850 and approximately 1000nm bands observed in Martian reflectivity spectra. Manicouagan data also show that possible assignments for intermediate band positions (900-920 nm) in Martian spectra are pyroxene and/or hematite-pyroxene assemblages. By analogy with impact melt sheets and in agreement with observables for Mars, oxidative alteration of Martian impact melt sheets above 250 C and subsequent erosion could produce rocks and soils with variable proportions of hematite (both bulk and nanophase), pyroxene, and phyllosilicates as iron-bearing mineralogies. If this process is dominant, these phases on Mars were formed rapidly at relativly high temperatures on a sporadic basis throughout the history of the planet. The Manicouagan samples also show that this mineralogical diversity can be accomplished at constant chemical composition, which is also indicated for Mars from the analyses of soil at the two Viking landing sites.

Morris, Richard V.↗

Hypervelocity impacts and magnetization of small bodies in the Solar System

The observed magnetism of asteroids such as Gaspra and Ida (and other small bodies in the solar system including the Moon and meteorites) may have resulted from an impact-induced shock wave producing a thermodynamic state in which iron-nickel alloy, dispersed in a silicate matrix, is driven from the usual low-temperature, low-pressure, alpha, kaemacite, phase to the paramagnetic, epsilon (hcp), phase. The magnetization was acquired upon rarefaction and reentry into the ferromagnetic, alpha, structure. The degree of remagnetization depends on the strength of the ambient field, which may have been associated with a Solar-System-wide magnetic field. A transient field induced by the impact event itself may have resulted in a significant, or possibly, even a dominant contribution, as well. The scaling law of Housen et al. (Housen, K. R., R. M. Schmidt, and K. A. Holsapple 1991) for catastrophic asteroid impact disaggregation imposes a constraint on the degree to which small planetary bodies may be magnetized and yet survive fragmentation by the same event. Our modeling results show it is possible that Ida was magnetized when a large impact fractured a 125 +/- 22-km-radius protoasteroid to form the Koronis family. Similarly, we calculate that Gaspra could be a magnetized fragment of a 45 +/- 15 km-radius protoasteroid.

Chen, Guangqing↗

Mechanism of phosphorescence quenching in photomagnetic molecules determined by positron annihilation spectroscopy

Platinum Octaethyl Porphyrin (Pt.OEP) is an efficient phosphor under ultraviolet excitation. The phosphorescent triplet state (T(sub 1)) is readily quenched by the oxygen (O2) molecules. This phenomenon is being utilized as the basis for global air pressure measurements in aerodynamic facilities at various laboratories. The exact mechanism by which O2 molecules quench the (T(sub 1)-S(sub 0)) transitions is still unknown. The diamagnetic S(sub n) singlet states, which feed T(sub 1) states via intersystem crossings, would presumably not be affected by O2. It must be the magnetic T(sub 1) states, which can interact with the paramagnetic O2 molecules, that are affected. However, our positron lifetime and Doppler broadening studies suggest the formation of (S(sub n).02) complexes which can also eventually reduce the population of the T(sub 1) states (i.e. quench phosphorescence). This is possible since higher triplet states in (Pt-OEP) are admixed with the S(sub n) states via spin orbit interactions. The experimental procedures and the results of various measurements are discussed in this paper.

Singh, Jag J.↗

Mechanism of phosphorescence quenching in photomagnetic molecules determined by positron annihilation spectroscopy

Platinum Octaethyl Porphyrin (Pt.OEP) is an efficient phosphor under ultraviolet excitation. The phosphorescent triplet state (T(sub 1)) is readily quenched by the oxygen (O2) molecules. This phenomenon is being utilized as the basis for global air pressure measurements in aerodynamic facilities at various laboratories. The exact mechanism by which O2 molecules quench the (T(sub 1) - S(sub 0)) transitions is still unknown. The diamagnetic S(sub n) singlet states, which feed T(sub 1) states via intersystem crossings, would presumably not be affected by O2. It must be the magnetic T(sub 1) states, which can interact with the paramagnetic O2 molecules, that are affected. However, our positron lifetime and Doppler broadening studies suggest the formation of (S(sub n) central dot O2) complexes which can also eventually reduce the population of the T(sub 1) states (i.e. quench phosphorescence). This is possible since higher triplet states in (Pt.OEP) are admixed with the S(sub n) states via spin orbit interactions. The experimental procedures and the results of various measurements are discussed in this paper.

Singh, Jag J.↗

Investigation of Oxygen-Induced Quenching of Phosphorescence in Photoexcited Aromatic Molecules by Positron Annihilation Spectroscopy

Platinum OctaEthyl Porphyrin (Pt.OEP) is an efficient phosphor under ultraviolet excitation. The phosphorescent triplet state P(T(Sup 1)) is readily quenched by the oxygen O2 molecules. This phenomenon is being utilized as the basis for global air pressure measurements in aerodynamic facilities at various laboratories. The exact mechanism by which O2 molecules quench the P(T(Sup 1) approaches P(S(Sub O)) transitions is still unknown. The diamagnetic singlet states P(S(Sub n)), which feed P(T(Sub 1)) states via intersystem crossings, would presumably not be affected by O2. It must be only the magnetic P(T(Sub 1)) states, which can interact with the paramagnetic O2 molecules, that are affected. However, our positron lifetime and Doppler broadening studies suggest the formation of O2P(S(Sub n)), complexes which can also eventually reduce the population of the P(T(Sub 1)) states (i.e., quench phosphorescence). This reduction is possible because higher triplet states in (Pt.OEP) are admixed with the P(S(Sub 1)), states via spin orbit interactions. The experimental procedures and the results of various measurements are presented in this paper.

Singh, Jag J.↗

Vapor Deposits in the Lunar Regolith

Since the Apollo missions, we have emphasized the following points, which are based on theoretical calculations and on laboratory studies of the properties of evaporated silicate deposits and of lunar samples. The mass of vapor generated by impacts on the lunar surface is comparable in magnitude to the mass of impact melt glasses; the physics of impact into a porous regolith requires that much of this vapor be retained in the soil rather than lost to space (as is widely believed); experimental coatings made from vaporized or sputtered lunar basalt contain abundant inclusions of submicroscopic, super paramagnetic metallic Fe; and this Fe may explain the magnetic signature, low albedo, reddened spectrum, and subdued absorption bands of lunar regolith. Our conclusions have been generally rejected by the lunar geochemical community for two reasons: there seemed to be no direct evidence for vapor deposits in Apollo samples, and it seemed that the lunar optical properties could be explained by the presence of impact melt glasses alone. However, advances in our understanding of the optical properties of glasses and of light scattering by planetary regoliths, and now the direct detection of vapor deposits, show that these objections are not valid. Vapor phase transport is a major process on the lunar surface, and unless its effects are taken into account, the chemical, magnetic, and optical properties of the regolith cannot be understood.

Hapke, Bruce↗

Development of a High-Resolution, Single-Photon X-Ray Detector

Research on the development of a low-temperature, magnetic bolometer for x-ray detection is reported. The principal accomplishments during the first phase of this research are as follows. (1) We have constructed SQUID magnetometers and detected both 122 keV and 6 keV x-rays in relatively larger metallic samples with high quantum efficiency. (2) The magnetic properties of a metal sample with localized paramagnetic spins have been measured and found to agree with theoretical expectations. (3) The size of the magnetic response of the sample to x-rays is in agreement with predictions based on the properties of the sample and sensitivity of the magnetometer, supporting the prediction that a resolution of 1 eV at 10 keV should be achievable.

Seidel, George M.↗

Hematite, pyroxene, and phyllosilicates on Mars: Implications from oxidized impact melt rocks from Manicouagan Crater, Quebec, Canada

Visible and near-IR reflectivity, Mossbauer, and X ray diffraction data were obtained on powders of impact melt rock from the Manicouagan Impact Crater located in Quebec, Canada. The iron mineralogy is dominated by pyroxene for the least oxidized samples and by hematite for the most oxidized samples. Phyllosilicate (smectite) contents up to 15 wt % were found in some heavily oxidized samples. Nanophase hematite and/or paramagnetic ferric iron is observed in all samples. No hydrous ferric oxides (e.g., goethite, lepidocrocite, and ferrihydrite) were detected, which implies the alteration occurred above 250 C. Oxidative alteration is thought to have occurred predominantly during late-stage crystallization and subsolidus cooling of the impact melt by invasion of oxidizing vapors and/or solutions while the impact melt rocks were still hot. The near-IR band minimum correlated with the extent of aleration (Fe(3+)/Fe(sub tot)) and ranged from approx. 1000 nm (high-Ca pyroxene) to approx. 850 nm (bulk, well-crystalline hematite) for least and most oxidized samples, respectively. Intermediate band positions (900-920 nm) are attributed to low-Ca pyroxene and/or a composite band from hematite-pyroxene assemblages. Manicouagan data are consistent with previous assignments of hematite and pyroxene to the 850 and 1000 nm bands observed in Martian reflectivity spectra. Manicouagan data also show that possible assignments for intermediate band positions (900-920 nm) in Martian spectra are pyroxene and/or hematite-pyroxene assemblages. By analogy with impact melt sheets and in agreement with observables for Mars, oxidative alteration of Martian impact melt sheets above 250 C and subsequent erosion could produce rocks and soils with variable proportions of hematite (both bulk and nanophase), pyroxene, and phyllosilicates as iron-bearing mineralogies. If this process is dominant, these phases on Mars were formed rapidly at relatively high temperatures on a sporadic basis throughout the history of the planet. The Manicouagan samples also show that this mineralogical diversity can be accomplished at constant chemical composition, which is also indicated for Mars from analyses of soil at the two Viking landing sites.

Morris, Richard V.↗

Electron Spin Resonance (ESR) Studies of Returned Comet Nucleus Samples

Electron Spin Resonance (ESR) studies have been carried out on organic and inorganic free radicals generated by gamma-ray and/or UV-irradiation and trapped in ice matrices. It is suggested that the concentration of these free radicals together with their thermal stability can be used as an accurate built-in geothermometer and radiation probe for returned comet nucleus sample studies. ESR studies have also been carried out on paramagnetic (Mn(2+), Ti(3+), and Fe(3+)) and ferromagnetic (ferric oxide and metallic iron) centers known to be present in terrestrial and extraterrestrial samples. The presence or absence of these magnetic centers coupled with their characteristic ESR lineshape can be used to investigate the shock effects, quenching/cooling rate and oxidation-reduction conditions in the formation and subsequent evolution of returned comet nucleus samples.

Tsay, Fun-Dow↗

Mesospheric Observations and Modeling of the Zeeman Split 233.9 GHz O-18O-16 line

Observations made from Kitt Peak, AZ, of the 233.9 GHz emission line of O-18O-16 in the upper stratosphere and lower mesosphere are reported. A good model fit to the line is obtained by incorporation of pressure and temperature broadening effects, as well as a Zeeman splitting algorithm that uses a standard geomagnetic field model and a paramagnetic Hamiltonian description of the molecular energy states. These observations are used, along with the well known O-18O-16 mixing ratio, to establish absolute calibration for observations of other chemical species from Kitt Peak. Repeated measurements show no change in this absolute calibration between observation dates. The wide magnetic splitting (+/-1.8 MHz) exhibited by this line with only six Zeeman components provides a unique test of middle atmosphere Zeeman effect model calculations, supporting the use Of 02 lines by microwave atmospheric sounders to measure pressure and temperature.

Sandor, Brad J.↗

Exploiting the Temperature/Concentration Dependence of Magnetic Susceptibility to Control Convection in Fundamental Studies of Solidification Phenomena

The objective of this new research project is to demonstrate by experiment, supplemented by mathematical modeling and physical property measurement, that the effects of buoyancy driven convection can be largely eliminated in ground-based experiments, and further reduced in flight, by applying a new technique. That technique exploits the dependence of magnetic susceptibility on composition or temperature. It is emphasized at the outset that the phenomenon to be exploited is fundamentally and practically different from the magnetic damping of convection in conducting liquids that has been the subject of much prior research. The concept suggesting this research is that all materials, even non-conductors, when placed in a magnetic field gradient, experience a force. Of particular interest here are paramagnetic and diamagnetic materials, classes which embrace the "model alloys", such as succinonitrile-acetone, that have been used by others investigating the fundamentals of solidification. Such alloys will exhibit a dependence of susceptibility on composition. The consequence is that, with a properly oriented field (gradient) a force will arise that can be made to be equal to, but opposite, the buoyancy force arising from concentration (or temperature) gradients. In this way convection can be stilled. The role of convection in determining the microstructure, and thereby properties, of materials is well known. Elimination of that convection has both scientific and technological consequences. Our knowledge of diffusive phenomena in solidification, phenomena normally hidden by the dominance of convection, is enhanced if we can study solidification of quiescent liquids. Furthermore, the microstructure, microchemistry and properties of materials (thereby practical value) are affected by the convection occurring during their solidification. Hitherto the method of choice for elimination of convection has been experimentation in microgravity. However, even in low Earth orbit, residual convection has effects. That residual convection arises from acceleration (drag on the spacecraft), displacement from the center of mass or transients in the gravitational field (g-jitter). There is therefore a need for both further reducing buoyancy driven flow in flight and allowing the simulation of microgravity during ground based experiments. Previous investigations, the research project description, theory behind the study and experimental methods as well as plots of magnetic fields and forces are presented.

Evans, J. W.↗

Magnetically Actuated Propellant Orientation, Controlling Fluids in a Low-Gravity Environment

Cryogenic fluid management (CFM) is a technology area common to virtually every space transportation propulsion concept envisioned. Storage, supply, transfer and handling of sub-critical cryogenic fluids are basic capabilities that have long been needed by multiple programs and the need is expected to continue in the future. The use of magnetic fields provides another method, which could replace or augment current/traditional approaches, potentially simplifying vehicle operational constraints. The magnetically actuated propellant orientation (MAPO) program effort focused on the use of magnetic fields to control fluid motion as it relates to positioning (i.e. orientation and acquisition) of a paramagnetic substance such as LO2. Current CFM state- of-the-art systems used to control and acquire propellant in low gravity environments rely on liquid surface tension devices which employ vanes, fine screen mesh channels and baskets. These devices trap and direct propellant to areas where it's needed and have been used routinely with storable (non-cryogenic) propellants. However, almost no data exists r,egarding their operation in cryogenics and the use of such devices confronts designers with a multitude of significant technology issues. Typical problems include a sensitivity to screen dry out (due to thermal loads and pressurant gas) and momentary adverse accelerations (generated from either internal or external sources). Any of these problems can potentially cause the acquisition systems to ingest or develop vapor and fail. The use of lightweight high field strength magnets may offer a valuable means of augmenting traditional systems potentially mitigating or at least easing operational requirements. Two potential uses of magnetic fields include: 1) strategically positioning magnets to keep vent ports clear of liquid (enabling low G vented fill operations), and 2) placing magnets in the center or around the walls of the tank to create an insulating vapor pocket (between the liquid and the tank wall) which could effectively lower heat transfer to the liquid (enabling increased storage time).

Martin, James J.↗