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Freund, F.

Publications and source records attributed to Freund, F..

Stress-Dependent Voltage Offsets From Polymer Insulators Used in Rock Mechanics and Material Testing

Dielectric insulators are used in a variety of laboratory settings when performing experiments in rock mechanics, petrology, and electromagnetic studies of rocks in the fields of geophysics,material science, and civil engineering. These components may be used to electrically isolate geological samples from the experimental equipment, to perform a mechanical compliance function between brittle samples and the loading equipment, to match ultrasonic transducers, or perform other functions. In manyexperimental configurations the insulators bear the full brunt of force applied to the sample but do not need to withstand high voltages, therefore the insulators are often thin sheets of mechanically tough polymers. From an instrument perspective, transduction from various types of mechanical perturbation has beenqualitatively compared for a number of polymers [1, 2] and these error sources are readily apparent duringhigh-impedance measurements if not mitigated. However even when following best practices, a force dependent voltage signal still remains and its behavior is explored in this presentation. In this experimenttwo thin sheets (0.25 mm) of high-density polyethylene (HDPE) were set up in a stack, held alternatelybetween three aluminum bars; this stack was placed on the platen of a 60T capacity hydraulic testingmachine. The surface area, A, over which the force is applied to the PE sheets in this sandwich is roughly 40 square cm, each sheet forming a parallel-plate capacitor having roughly 320 pF [3], assuming therelative dielectric permittivity of PE is approximately 2.3. The outer two aluminum bars were connected to the LO input ofthe electrometer and the central aluminum bar was connected to the HI input of a Keithley model 617 electrometer. Once the stack is mechanically well-seated with no air gaps, the voltage offset is observed tobe a linear function of the baseline voltage for a given change in applied force. For a periodically appliedforce of 66.7 kN the voltage offsets were measured as a function of initial voltage, and these data were fitwith a linear function that was constrained to pass through the origin. The best fit solution had a correlation coefficient of R=0.85 and a slope of approximately -0.0228 volts/volt. The voltage offset when normalizedis demonstrated to be constant -2.28% for both positive and negative polarities over nearly 3 orders ofbaseline voltage magnitude. From this, the voltage-force coefficient is derived to be -0.34 ppm/N. Thiscorrelates well to a first-order parallel plate capacitor model that assumes constant area, and smalldeformation such that the polymer may be mechanically modeled by a spring that obeys Hookes law. Thissimple model predicts that the coefficient of proportionality is a function of Youngs modulus E= 0.8 GPaand surface area of the insulator, theoretically -1EA= -0.31 ppm/N. The outcome of this work is animproved insulator made from ultra-high molecular weight (UHMW) polyethylene and other approachestoward the minimization of and compensation for these experimental artifacts.

Electromagnetic Studies of Rocks

Antipodal Magnetic Anomalies on the Moon, Contributions from Impact Induced Currents Due to Positive Holes and Flexoelectric Phenomina and Dynamo

Large impacts on the Moon generate large pressure pulses that penetrate the whole body. Several of these large impacts may have generated antipodal structure with anomalous magnetic intensity.These regions can be more than a thousand km across, with fields of the order of tens to hundreds of nT. This is the case of Orientale, Imbrium, Serenitatis, Crisium, and Nectaris impact basins. The production of large-scale magnetic fields and associated crustal magnetization due to lunar basin-forming impacts was hypothesized to have an origin in fields external to the impact plasma cloud that are produced by the magnetohydrodynamic interaction of the cloud with ambient magnetic fields and plasmas. During the period of compressed antipodal field amplification, seismic compressional waves from the impact converge at the antipode resulting in transient shock pressures that reach 2 GPa (20 kbar). This can produce conditions for shock magnetic acquisition of the crust antipodal to impact basins.

Kletetschka, G.

Satellite Infrared Radiation Measurements Prior to the Major Earthquakes

This work describes our search for a relationship between tectonic stresses and increases in mid-infrared (IR) flux as part of a possible ensemble of electromagnetic (EM) phenomena that may be related to earthquake activity. We present and &scuss observed variations in thermal transients and radiation fields prior to the earthquakes of Jan 22, 2003 Colima (M6.7) Mexico, Sept. 28 .2004 near Parkfield (M6.0) in California and Northern Sumatra (M8.5) Dec. 26,2004. Previous analysis of earthquake events has indicated the presence of an IR anomaly, where temperatures increased or did not return to its usual nighttime value. Our procedures analyze nighttime satellite data that records the general condtion of the ground after sunset. We have found from the MODIS instrument data that five days before the Colima earthquake the IR land surface nighttime temperature rose up to +4 degrees C in a 100 km radius around the epicenter. The IR transient field recorded by MODIS in the vicinity of Parkfield, also with a cloud free environment, was around +1 degree C and is significantly smaller than the IR anomaly around the Colima epicenter. Ground surface temperatures near the Parkfield epicenter four days prior to the earthquake show steady increase. However, on the night preceding the quake, a significant drop in relative humidity was indicated, process similar to those register prior to the Colima event. Recent analyses of continuous ongoing long- wavelength Earth radiation (OLR) indicate significant and anomalous variability prior to some earthquakes. The cause of these anomalies is not well understood but could be the result of a triggering by an interaction between the lithosphere-hydrosphere and atmospheric related to changes in the near surface electrical field and/or gas composition prior to the earthquake. The OLR anomaly usually covers large areas surrounding the main epicenter. We have found strong anomalies signal (two sigma) along the epicentral area signals on Dec 21, five days prior to the Northern Sumatra quake compared to the reference field for December 2001-2004 periods. Our recent results support the hypothesis of a possible relationship between a thermodynamic processes produced by increasing tectonic stress in the Earth's crust and a subsequent electro-chemical interaction between this crust and the atmosphere/ionosphere.

Ouzounov, Dimitar

Carboxylic and dicarboxylic acids extracted from crushed magnesium oxide single crystals

Carboxylic and dicarboxylic acids (glycolic, oxalic, malonic and succinic) have been extracted with tetrahydrofuran (THF) and H2O from large synthetic MgO crystals, crushed to a medium fine powder. The extracts were characterized by infrared spectroscopy and 1H-NMR. The THF extracts were derivatized with tert-butyldimethylsilyl (t-BDMS) for GC-MS analysis. A single crystal separated from the extract was used for an x-ray structure analysis, giving the monoclinic unit cell, space group P21/c with ao = 5.543 A, bo = 8.845 A, co = 5.086 A, and beta = 91.9 degrees, consistent with beta-succinic acid, HOOC(CH2)COOH. The amount of extracted acids is estimated to be of the order of 0.1 to 0.5 mg g-1 MgO. The MgO crystals from which these organic acids were extracted grew from the 2860 degrees C hot melt, saturated with CO/CO2 and H2O, thereby incorporating small amounts of the gaseous components to form a solid solution (ss) with MgO. Upon cooling, the ss becomes supersaturated, causing solute carbon and other solute species to segregate not only to the surface but also internally, to dislocations and subgrain boundaries. The organic acids extracted from the MgO crystals after crushing appear to derive from these segregated solutes that formed C-C, C-H and C-O bonds along dislocations and other defects in the MgO structure, leading to entities that can generically be described as (HxCyOz)n-. The processes underlying the formation of these precursors are fundamental in nature and expected to be operational in any minerals, preferentially those with dense structures, that crystallized in H2O-CO2-laden environments. This opens the possibility that common magmatic and metamorphic rocks when weathering at the surface of a tectonically active planet like Earth may be an important source of abiogenically formed complex organic compounds.

NASA Discipline Exobiology

Crystal-field-driven redox reactions: How common minerals split H2O and CO2 into reduced H2 and C plus oxygen

It is difficult to prove the presence of molecular H2 and reduced C in minerals containing dissolved H2 and CO2. A technique was developed which unambiguously shows that minerals grown in viciously reducing environments contain peroxy in their crystal structures. The peroxy represent interstitial oxygen atoms left behind when the solute H2O and/or CO2 split off H2 and C as a result of internal redox reactions, driven by the crystal field. The observation of peroxy affirms the presence of H2 and reduced C. It shows that the solid state is indeed an unusual reaction medium.

Freund, F.

Positive holes in magnesium oxide - Correlation between magnetic, electric, and dielectric anomalies

The present magnetic susceptibility investigation of high purity MgO single crystals notes an anomally at 800 K which is associated with increasing electrical conductivity, a rise in static dielectric constant from 9 to 150, and the appearance of a pronounced positive surface charge. These phenomena can be accounted for in terms of peroxy defects which represent self-trapped, spin-paired positive holes at Mg(2+) vacancy sites. The holes begin to decouple their spins above 600 K.

Batllo, F.

Low-pressure clathrate-hydrate formation in amorphous astrophysical ice analogs

In modeling cometary ice, the properties of clathrate hydrates were used to explain anomalous gas release at large radial distances from the Sun, and the retention of particular gas inventories at elevated temperatures. Clathrates may also have been important early in solar system history. However, there has never been a reasonable mechanism proposed for clathrate formation under the low pressures typical of these environments. For the first time, it was shown that clathrate hydrates can be formed by warming and annealing amorphous mixed molecular ices at low pressures. The complex microstructures which occur as a result of clathrate formation from the solid state may provide an explanation for a variety of unexplained phenomena. The vacuum and imaging systems of an Hitachi H-500H Analytical Electron Microscope was modified to study mixed molecular ices at temperatures between 12 and 373 K. The resulting ices are characterized by low-electron dose Transmission Electron Microscopy (TEM) and Selected Area Electron Diffraction (SAED). The implications of these results for the mechanical and gas release properties of comets are discussed. Laboratory IR data from similar ices are presented which suggest the possibility of remotely observing and identifying clathrates in astrophysical objects.

Blake, D. F.

Clathrate type 2 hydrate formation in vacuo under astrophysical conditions

The properties of clathrate hydrates were used to explain the complex and poorly understood physical processes taking place within cometary nuclei and other icy solar system bodies. Most of all the experiments previously conducted used starting compositions which would yield clathrate types I hydrates. The main criterion for type I vs. type II clathrate hydrate formation is the size of the guest molecule. The stoichiometry of the two structure types is also quite different. In addition, the larger molecules which would form type II clathrate hydrates typically have lower vapor pressures. The result of these considerations is that at temperatures where we identified clathrate formation (120-130 K), it is more likely that type II clathrate hydrates will form. We also formed clathrate II hydrates of methanol by direct vapor deposition in the temperature range 125-135 K.

Blake, D. F.

Dissociation of O(2-)2 defects into paramagnetic O(-) in wide band-gap insulators - A magnetic susceptibility study of magnesium oxide

The magnetic susceptibility of single-crystal MgO has been measured in the temperature range 300-1000 K, using a Faraday balance. The high-purity crystal (less than 100 ppm transition metals), grown from the melt in a H2O-containing atmosphere, was found to be paramagnetic due to the presence of defects on the O(2-) sublattice. The defects derive from OH(-) introduced into the MgO matrix by the dissolution of traces of H2O during crystal growth. The OH(-) converts into O(2-)2 and H2. Each O(2-)2 represents two coupled, spin-paired O(-) states. The observed strongly temperature-dependent paramagnetism can be described by three contributions that overlay the intrinsic diamagnetism of MgO and arise from the low level of transition-metal impurities, O(-) generated by 0(2-)2 dissociation, and O(-) states trapped by quenching from high temperatures from previous experiments.

Batllo, F.

O(-) identified at high temperatures in CaO-based catalysts for oxidative methane dimerization

A technique called charge-distribution analysis (CDA) is employed to study mobile charge carriers in the oxidation catalysts CaO, CaO with 11 percent Na2O, and CaO with 10 percent La2O3. A threshold temperature of about 550-600 C is identified at which highly mobile charge carriers are present, and the CDA studies show that they are O(-) states. The present investigation indicates the usefulness of CDA in catalysis research with pressed powder samples and gas/solid reactions.

Freund, F.

The emission of atoms and molecules accompanying fracture of single-crystal MgO

The emission of particles due to deformation and fracture of materials has been investigated. The emission of electrons (exoelectron emission), ions, neutral species, photons (triboluminescence), as well as long wavelength electromagnetic radiation was observed; collectively these emissions are referred to as fractoemission. This paper describes measurements of the neutral emission accompanying the fracture of single-crystal MgO. Masses detected are tentatively assigned to the emission of H2, CH4, H2O, CO, O2, CO2, and atomic Mg. Other hydrocarbons are also observed. The time dependencies of some of these emissions relative to fracture are presented for two different loading conditions.

Dickinson, J. T.

Carbon in oxides and silicates - Dissolution versus exsolution

A theory of CO2 dissolution in the solid state is developed, using the idea proposed by Freund (1983) concerning dissolution of CO/CO2 in MgO on the basis of their experimental results obtained with an MgO-containing carbon impurity. It is shown that the dissolution mechanism may be linked to an internal redox reaction by which a certain number of lattice oxygens change their formal oxidation state from -2 to -1, while the carbon becomes reduced. The similarities between the mechanisms of CO and/or CO2 dissolution and that of H2O dissolution are pointed out. A hypothesis is proposed concerning the exsolution of reduced carbon from supersaturated solid solutions under conditions which permit C-C bond formation.

Freund, F.

Presence, segregation and reactivity of H, C and N dissolved in some refractory oxides

The sources of impurities, particularly carbon, in high melting oxides and silicates are discussed, along with detection and quantification methods. The impurities are important for their effects on bulk material properties through the media of, e.g., surface or grain boundary characteristics. The impurities are usually encountered by the contact of the oxide (refractory) material with volatiles such as H2O and CO2, which become incorporated in the material and form anion complexes with oxygen acting as a covalent bonded ligand. The specific processes undergone by MgO in assimilating C impurities are delineated, using data obtained with X-ray photoelectron spectroscopy, Auger electron spectroscopy, secondary ion mass spectrometry and nuclear reaction profiling. Finally, maintenance of a supersaturated solid solution with C impurities by space charge control is described as a means of offset impurity effects.

Freund, F.