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At least 667 records · Page 37

Evolution of the Oxidation State of the Earth's Mantle: Challenges of High Pressure Quenching

The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3+ at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. Experiments of more mafic compositions and at higher pressures commonly form a polyphase quench intergrowth composed primarily of pyroxenes, with interstitial glass which hosts nearly all of the more volatile minor elements. In our previous experiments on shergottite compositions, variable fO2, T, and P is less than 4 GPa, Fe3+/TotFe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3+/TotFe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3+. Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Experiments with Knippa basalt as the starting composition were conducted at 1-8 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products from 7-8 GPa quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal Fe3+/2+. A number of different approaches have been employed to produce glassy samples that can be measured by EELS and XANES. A more intermediate andesite was used in one experiment, and decompression during quenching was attempted after, but both resulted in a finer grained polyphase texture. Experiments are currently underway to test different capsule materials may affect quench texture. A preliminary experiment using liquid nitrogen to greatly enhance the rate of cooling of the assembly has also been attempted and this technique will be refined in further experiments.

Danielson, L. R.↗

Development and Application of Tools to Characterize the Oxidative Degradation of AP/HTPB/Al Propellants in a Propellant Reliability Study

The oxidative thermal aging of a crosslinked hydroxyl-terminated polybutadiene (HTPB)/isophorone diisocyanate (IPDI) polyurethane rubber was studied at temperatures between 25 C and 125 C. Changes in tensile elongation, mechanical hardening, polymer network properties, density, O2 permeation, and molecular chain dynamics were investigated as a function of age. The techniques used include solvent swelling, detailed modulus profiling, and NMR relaxation measurements. The Arrhenius methodology, which normally assumes a linear extrapolation of high temperature aging data, is critically evaluated by using extensive data superposition and highly sensitive oxygen consumption measurements. Significant curvature in the Arrhenius diagram of these oxidation rates is observed to be similar to previous results found for other rubber materials that have been evaluated by this technique. Preliminary gel/network properties suggest that crosslinking is the dominant process at higher temperatures. The effect on the oxidation rate of the binder when other constituents found in propellants are present, such as ammonium perchlorate, plasticizer and aluminum powder, is presented.

Celina, Mathew↗

Producing Next Generation Superalloys Through Advanced Characterization and Manufacturing Techniques

NASA is currently working towards developing the next generation high temperature alloys for various aerospace and energy applications. Through advanced microscopy and computational insights, a novel atomic scale strengthening mechanism was discovered in Ni-base superalloys. This new local phase transformation strengthening technique has been successfully implemented resulting in new disk alloys with substantial improvements in creep strength over current state-of-the-art. Furthermore, additive manufacturing has been leveraged to produce dispersion strengthened (DS), multi-principal element alloys (MPEA) without the use of traditional mechanical alloying or chemical reactions. This new processing technique has successfully resulted in 99.9% dense oxide dispersion strengthened NiCoCr alloy parts. High temperature mechanical testing of the DS alloys showed significant improvements in strength and ductility over the baseline NiCoCr. As a result, this recently discovered processing route opens a new alloy design and production path that is synergistic between additive manufacturing and dispersion strengthening, possibly enabling a new generation of high-performance alloys.

Smith, Timothy M.↗

Characterization and properties of controlled nucleation thermochemical deposited (CNTD) silicon carbide

The microstructure of controlled nucleation thermochemical deposition (CNTD) - SiC material was studied and the room temperature and high temperature bend strength and oxidation resistance was evaluated. Utilizing the CNTD process, ultrafine grained (0.01-0.1 mm) SiC was deposited on W - wires (0.5 mm diameter by 20 cm long) as substrates. The deposited SiC rods had superior surface smoothness and were without any macrocolumnar growth commonly found in conventional CVD material. At both room and high temperature (1200 - 1380 C), the CNTD - SiC exhibited bend strength approximately 200,000 psi (1380 MPa), several times higher than that of hot pressed, sintered, or CVD SiC. The excellent retention of strength at high temperature was attributed to the high purity and fine grain size of the SiC deposit and the apparent absence of grain growth at elevated temperatures. The rates of weight change for CNTD - SiC during oxidation were lower than for NC-203 (hot pressed SiC), higher than for GE's CVD - SiC, and considerably below those for HS-130 (hot pressed Si3N4). The high purity, fully dense, and stable grain size CNTD - SiC material shows potential for high temperature structural applications; however problem areas might include: scaling the process to make larger parts, deposition on removable substrates, and the possible residual tensile stress.

Dutta, S.↗

The Use of Tribocharging in the Electrostatic Beneficiation of Lunar Simulant

Any future lunar base and habitat must be constructed from strong dense materials in order to provide for thermal and radiation protection. Lunar soil may meet this need. Lunar regolith has high concentrations of aluminum, silicon, calcium, iron, sodium, and titanium oxides. Refinement or enrichment of specific minerals in the soil before it is chemically processed may be more desirable as it would reduce the size and energy requirements required to produce the virgin material and it may significantly reduce the process' complexity. Also, investigations into the potential production of breathable oxygen from oxidized mineral components are a major research initiative by NASA. In this study. the objective was to investigate the use of tribocharging to charge lunar simulants and pass them through a parallel plate separator to enrich different mineral fractions. This technique takes advantage of the high Lunar vacuum in which much higher voltages can be used on the separation plates than in air. Additionally, the Lunar g1avity, only being 1/6 that of Earth, allows the particles more separation time between the plates and therefore enhances separation. For the separation studies, two lunar stimulants were used. The first simulant was created in-house, labeled KSC-1. using commercially supplied (sieved to 325 mesh) materials, and was composed of 40 wt. % feldspar ((Na,K,Ca)AlSi3O8;SiO2), 40 wt. % olivine ((Mg,Fe)2SiO4), 10 wt. % ilmenite (FeTiO3). and 10 wt. % spodumene (LiAlSi2O6) (pyroxene). The advantage of the in-house mixture is that the composition can he varied to simulate different soil compositions from different areas on the moon. This simulant was used to show proof-of-concept using the designed separator in air. The second stimulant was JSC-1. used for the vacuum experiments. JSC-1 is principally basalts, containing phases of plagioclase. pyroxene. olivine, and ilmenite. The JSC-1 was sieved to provide a 50-75 micron size range to correlate with the mean grain size found on the moon's surface [1]. Four different materials were investigated for the triboelectrification process; aluminum, copper. stainless steel, and PTFE. These materials were selected because they offer a wide variation in work functions (aluminum 4.28 eV, copper 4.65 eV. stainless steel 5.04 eV, and PTFE 5.75 eV). The difference between the work function of each material and the simulant influences the charge obtained by the grains. Each simulant was analyzed before and after separation using X-ray Photoelectron Spectroscopy (XPS) to determine mineral surface composition. In addition. Raman spectroscopy was performed on the JSC-1 before and after separation in vacuum to determine the mineral composition. Charge-to-mass (Q/M) measurements were performed using a fluidizing bed in air and passing the simulant through a static mixer of a particular material and collecting it in a Faraday pail grounded through an electrometer. To measure the Q/M in vacuum, a special device was constructed consisting of a heater/shaker cup that fed into a solid block of material (either PTFE, copper, or aluminum) in which a channel composed of a "zig-zag" series of inclines greater than 50 degrees has been cut. The voltage to the vibrating motor can be varied to control the amount of simulant passing through the channel. Figure I shows the Q/M measurements for JSC-1 tribocharged using the static mixers and the incline plane chargers in air, and the incline plane chargers in vacuum.

Trigwell, S.↗

Mechanistic studies of the CO-oxidation reaction on catalysts for use in long-life CO2 lasers

The catalytic recombination of carbon monoxide and oxygen was studied under conditions expected to be present in a sealed E-beam CO2 laser system. These conditions are typically a gas inlet temperature of 60 C, a substoichiometric CO/O2 ratio of ca. 2.5/1 with an oxygen feed rate of ca. 5 micromoles/s, a carrier gas comprising He, N2 and CO2 in the ratio of 3:2:1, near atmospheric pressure and a gas velocity of 4 m/s. Heterogeneous catalysts, based on precious metal supported on tin oxide, have been coated onto ceramic monoliths and tested for catalytic activity and stability after a reduction/passivation step. Two catalyst systems have been chosen. These are Pt/Pd/SnO2 and Pt/Ru/SnO2. Under the conditions described above, a characteristic decline in catalytic activity is apparent for both systems, and exit gas temperature has been recognized as a sensitive parameter by which to monitor the activity changes. A semilogarithmic plot of exit temperature as a function of time has revealed two distinct processes connected with the decline in activity: one process is associated with reduction of the oxidized precious metal (at Site A), whilst the other is related to the formation and approach to steady-state of an active site at the metal/support interface (Site B).

Dawood, Talat↗

Windows(Registered Trademark)-Based Software Models Cyclic Oxidation Behavior

Oxidation of high-temperature aerospace materials is a universal issue for combustion-path components in turbine or rocket engines. In addition to the question of the consumption of material due to growth of protective scale at use temperatures, there is also the question of cyclic effects and spallation of scale on cooldown. The spallation results in the removal of part of the protective oxide in a discontinuous step and thereby opens the way for more rapid oxidation upon reheating. In experiments, cyclic oxidation behavior is most commonly characterized by measuring changes in weight during extended time intervals that include hundreds or thousands of heating and cooling cycles. Weight gains occurring during isothermal scale-growth processes have been well characterized as being parabolic or nearly parabolic functions of time because diffusion controls reaction rates. In contrast, the net weight change in cyclic oxidation is the sum of the effects of the growth and spallation of scale. Typically, the net weight gain in cyclic oxidation is determined only empirically (that is, by measurement), with no unique or straightforward mathematical connection to either the rate of growth or the amount of metal consumed. Thus, there is a need for mathematical modeling to infer spallation mechanisms. COSP is a computer program that models the growth and spallation processes of cyclic oxidation on the basis of a few elementary assumptions that were discussed in COSP: A Computer Model of Cyclic Oxidation, Oxidation of Metals, vol. 36, numbers 1 and 2, 1991, pages 81-112. Inputs to the model include the selection of an oxidation-growth law and a spalling geometry, plus oxide-phase, growth-rate, cycle-duration, and spall-constant parameters. (The spalling fraction is often shown to be a constant factor times the existing amount of scale.) The output of COSP includes the net change in weight, the amounts of retained and spalled oxide, the total amounts of oxygen and metal consumed, and the terminal rates of weight loss and metal consumption.

Smialek, J. L.↗

Oxidation-induced contraction and strengthening of boron fibers

An investigation was conducted to measure and understand the physical and mechanical effects that occur in boron fibers during and after thermal treatment in a controlled oxygen argon gaseous mixture. Of principal concern was the optimization of this treatment as a secondary processing method for significantly improving fiber tensile strength. Strengthening was accomplished by an oxidation induced axial contraction of the fiber and a resulting axial compression of strength limiting flaws within the fiber's tungsten boride core. Various physical observations were used to develop mechanistic models for oxidation, contraction, and flow formation. Processing guidelines are discussed for possibly exceeding the 5.5 GN/sq m strength limit and also for achieving fiber strengthening during application of boron containing diffusion barrier coatings.

Dicarlo, J. A.↗

Noninvasive Breath Analysis Using NASA E-Nose Technology for Health Assessment

Clinical breath analysis is based on the fact that many important metabolites and biomarker molecules are present at detectable levels in exhaled breath, and many of these molecules correlate with human disease or correlate with physiological states that could lead to a decline in health. Presented is a technology that utilizes an array of chemical sensors combined with humidity, temperature and pressure for real time breath analysis to correlate the chemical information in the breath with the state and functioning of different human organs. For example, a marker for pulmonary inflammation processes of the lower respiratory tract, e.g. asthma, is the increase of the nitrogen oxide (NO) concentration in breath. Other volatile biomarkers may correlate with infectious process, metabolic conditions and inflammatory diseases, such as traumatic brain injury (TBI). This technology is also called "electronic nose" (E-Nose) in the sense that the device can mimic human nose to smell odors using a pattern recognition technique to analyze the sensor array data. Breath sampling is non-invasive and can be analyzed in real-time.

Li, Jing↗

Carbon Nanostructure: Its Evolution During its Impact Upon Soot Growth and Oxidation

The proposed work is a ground-based study to define and quantify soot nanostructural changes in response to growth conditions, thermal and oxidative treatments and to quantify their impact upon further oxidation and growth of highly ordered carbon materials. Experimental data relating soot oxidation rates to multiple oxidizing species concentrations will directly test for additive or synergistic soot oxidation rates. Such validation is central for assessing the applicability of individual soot oxidation rates and designing oxidative strategies for controlling soot loadings in and emissions from turbulent combustion processes. Through these experiments, new insights into soot nanostructure evolution during and its impact upon oxidation by O2 and OH will be realized. It is expected that the results of this effort will spawn new research directions in future microgravity and 1g environments. Issues raised by positive or even negative demonstration of the hypotheses of this proposal have direct bearing on modelling and controlling soot formation and its destruction in nearly every combustion process producing soot.

Source record↗

Research to Significantly Enhance Composites Survivability at 550 F in Oxidative Environments

Methylene dianiline (MDA) and its derivatives have been used in the synthesis of polyimides to yield polymers with characteristic low-density, high tensile strength, improved solubility in organic solvents, low-melt viscosities and high thermal stability (greater than 550 F) in air. Polyimides with such properties are desirable for use in aerospace systems, e.g., jet engines, airframe, missiles, and rockets where weight is critical. Recent research at Prairie View A&M University is focused on developing monomers to generate polyimides with enhanced performance over that of NASA s PMR-15. The objective of this work is to synthesize three ring aromatic diamines which are non-toxic and when reacted with the appropriate dianhydrides will yield polyimides with lower viscosity, improve processability, good retention of mechanical properties, and oxidative stability at high environmental temperatures. Modifications of the three ring aromatic diamines include replacing the methylene linkages with aromatic ethers by nucleophilic aromatic substitution reactions and incorporating mono- and di-substituents to the center aromatic ring. An update of current reactions involved in synthesis efforts to generate three ring aromatic monomers for polyimides with methylene, carbonyl, and ether linkages separating the aromatic moieties will be displayed.

Meador, Michael A.↗

40 Years of Processing Pieces of Space

This year marks the 40th year anniversary for the Antarctic Search for Meteorite (ANSMET) program. In 1976, the ANSMET program led the first expedition to Antarctica. The ANSMET program is a US-led field-based science project that recovers meteorite samples from Antarctica. Once a year from late November to late January, a field team consisting of 8 to 12 people, spends 6-8 weeks camping on the ice and collecting meteorites. Since 1976, more than 22,000 meteorite samples have been recovered. These meteorites come from asteroids, planets and other bodies of the solar system. Once collected, the Antarctic meteorites are shipped to NASA/Johnson Space Center (JSC) Houston, TX. in a refrigerated truck and are kept frozen to minimize oxidation until they are ready for initial processing. In Antarctica each meteorite is given a field tag which consists of numbers, once in the lab, this is replaced by an official tag, consisting of the Antarctic field location and year collected. The types and numbers of meteorites that have been classified include 849 carbonaceous chondrites, 135 enstatites, 512 achondrites, 64 stony, 115 irons, 48 others (27 R chondrites, 7 ungrouped), 6,161 H chondrites, 7,668 L chondrites, and 4,589 LL chondrites. Although 80-85 percent of the collected meteorites fall in the ordinary chondrite group, the other approximately 15 percent represent rare types of achondrites and carbonaceous chondrites. These rare meteorites include 25 lunar meteorites, 15 Martian meteorites, scores of various types of carbonaceous chondrites, and unique achondrites. The Antarctic meteorites that have been collected are processed in the Meteorite Processing Lab at JSC in Houston, TX. Initial processing of the meteorites begins with thawing/drying the meteorites in a nitrogen glove box for 24 to 48 hours. The meteorites are then photographed, measured, weighed and a description of the interior and exterior of each meteorite is written. The meteorite is broken and a representative sample, either a 1-3 gram chip or thin section is sent to the Smithsonian Institution for classification. After Antarctic meteorites have been classified and approved by the Nomenclature Committee of the Meteoritical Society, they are announced in the Antarctic Meteorite Newsletter, which is published twice per year (fall and spring) so that scientists may review which meteorites are available to study. Requests for Antarctic Meteorite samples are welcomed from research scientists, regardless of their current state of funding for meteorite studies. Since its inception over 3,300 requests have been made for pieces of these meteorites and over 400 investigators worldwide are active in the study of meteorites.. Research on these samples has been published in more than1500 peer reviewed articles; a listing of papers for any meteorite sample can be generated by accessing http://curator.jsc.nasa.gov/antmet/referencesearch.cfm. Antarctic meteorite samples requested by scientists are prepared several different ways. Most samples are prepared as chips, either using a rock splitter or using a chisel and chipping bowl. In special situations, a researcher may request a meteorite slab in which case the samples are cut using a diamond-bladed bandsaw inside of a dry nitrogen glove box. The meteorites are always cut in a 100 percent liquid-free environment. Additionally, thin/thick sections of Antarctic meteorites are also prepared at JSC. The meteorite thin section lab at JSC can prepare standard 30-micron thin sections, thick sections of variable thickness (100 to 200 microns), or demountable sections using superglue, all section are prepared without using water. Although many of the techniques used back in the '70's are still used today, advances in computers, software, databases, available tools and instrumentation have helped to streamline and shorten the duration of the classification process. In conjunction with present day missions to asteroids and other planets, meteorite studies have not only led to a better understanding of the complex histories of these bodies but have also tied certain meteorite groups to particular asteroid bodies. New meteorite discoveries by the ANSMET program provide a cost effective method for obtaining samples of previously unsampled bodies, allowing scientists to learn more about the origin, composition, and evolution of the solar system. Preservation in our cleanrooms at NASA allows material to be archived for future generations and advances in instrumentation and analysis.

Satterwhite, C. E.↗

Deep Etching Process Developed for the Fabrication of Silicon Carbide Microsystems

Silicon carbide (SiC), because of its superior electrical and mechanical properties at elevated temperatures, is a nearly ideal material for the microminiature sensors and actuators that are used in harsh environments where temperatures may reach 600 C or greater. Deep etching using plasma methods is one of the key processes used to fabricate silicon microsystems for more benign environments, but SiC has proven to be a more difficult material to etch, and etch depths in SiC have been limited to several micrometers. Recently, the Sensors and Electronics Technology Branch at the NASA Glenn Research Center at Lewis Field developed a plasma etching process that was shown to be capable of etching SiC to a depth of 60 mm. Deep etching of SiC is achieved by inductive coupling of radiofrequency electrical energy to a sulfur hexafluoride (SF6) plasma to direct a high flux of energetic ions and reactive fluorine atoms to the SiC surface. The plasma etch is performed at a low pressure, 5 mtorr, which together with a high gas throughput, provides for rapid removal of the gaseous etch products. The lateral topology of the SiC microstructure is defined by a thin film of etch-resistant material, such as indium-tin-oxide, which is patterned using conventional photolithographic processes. Ions from the plasma bombard the exposed SiC surfaces and supply the energy needed to initiate a reaction between SiC and atomic fluorine. In the absence of ion bombardment, no reaction occurs, so surfaces perpendicular to the wafer surface (the etch sidewalls) are etched slowly, yielding the desired vertical sidewalls.

Beheim, Glenn M.↗

Fuel Cell Propulsion Systems for an All-electric Personal Air Vehicle

There is a growing interest in the use of fuel cells as a power source for all-electric aircraft propulsion as a means to substantially reduce or eliminate environmentally harmful emissions. Among the technologies under consideration for these concepts are advanced proton exchange membrane and solid oxide fuel cells, alternative fuels and fuel processing, and fuel storage. This paper summarizes the results of a first-order feasibility study for an all-electric personal air vehicle utilizing a fuel cell-powered propulsion system. A representative aircraft with an internal combustion engine was chosen as a baseline to provide key parameters to the study, including engine power and subsystem mass, fuel storage volume and mass, and aircraft range. The engine, fuel tank, and associated ancillaries were then replaced with a fuel cell subsystem. Various configurations were considered including: a proton exchange membrane (PEM) fuel cell with liquid hydrogen storage; a direct methanol PEM fuel cell; and a direct internal reforming solid oxide fuel cell (SOFC)/turbine hybrid system using liquid methane fuel. Each configuration was compared to the baseline case on a mass and range basis.

Kohout, Lisa L.↗

Fuel Cell Propulsion Systems for an All-Electric Personal Air Vehicle

There is a growing interest in the use of fuel cells as a power source for all-electric aircraft propulsion as a means to substantially reduce or eliminate environmentally harmful emissions. Among the technologies under consideration for these concepts are advanced proton exchange membrane and solid oxide fuel cells, alternative fuels and fuel processing, and fuel storage. This paper summarizes the results of a first-order feasibility study for an all-electric personal air vehicle utilizing a fuel cell-powered propulsion system. A representative aircraft with an internal combustion engine was chosen as a baseline to provide key parameters to the study, including engine power and subsystem mass, fuel storage volume and mass, and aircraft range. The engine, fuel tank, and associated ancillaries were then replaced with a fuel cell subsystem. Various configurations were considered including: a proton exchange membrane (PEM) fuel cell with liquid hydrogen storage; a direct methanol PEM fuel cell; and a direct internal reforming solid oxide fuel cell (SOFC)/turbine hybrid system using liquid methane fuel. Each configuration was compared to the baseline case on a mass and range basis.

Kohout, Lisa L.↗

Synthesis and Stability of Iron Nanoparticles for Lunar Environment Studies

Simulant of lunar dust is needed when researching the lunar environment. However, unlike the true lunar dust, today s simulants do not contain nanophase iron. Two different processes have been developed to fabricate nanophase iron to be used as part of the lunar dust simulant: (1) Sequentially treating a mixture of ferric chloride, fluorinated carbon, and soda lime glass beads at about 300 C in nitrogen, at room temperature in air, and then at 1050 C in nitrogen. The product includes glass beads that are grey in color, can be attracted by a magnet, and contain alpha-iron nanoparticles (which seem to slowly lose their lattice structure in ambient air during a period of 12 months). This product may have some similarity to the lunar glassy regolith that contains Fe(sup 0). (2) Heating a mixture of carbon black and a lunar simulant (a mixed metal oxide that includes iron oxide) at 1050 C in nitrogen. This process simulates lunar dust reaction to the carbon in a micrometeorite at the time of impact. The product contains a chemically modified simulant that can be attracted by a magnet and has a surface layer whose iron concentration increased during the reaction. The iron was found to be alpha-iron and Fe3O4 nanoparticles, which appear to grow after the fabrication process, but stabilizes after 6 months of ambient air storage.

Hung, Ching-cheh↗

Characterization of silicon-gate CMOS/SOS integrated circuits processed with ion implantation

Progress in developing the application of ion implantation techniques to silicon gate CMOS/SOS processing is described. All of the conventional doping techniques such as in situ doping of the epi-film and diffusion by means of doped oxides are replaced by ion implantation. Various devices and process parameters are characterized to generate an optimum process by the use of an existing SOS test array. As a result, excellent circuit performance is achieved. A general description of the all ion implantation process is presented.

Woo, D. S.↗

Chemical reaction of atomic oxygen with evaporated films of copper, part 4

Evaporated copper films were exposed to an atomic oxygen flux of 1.4 x 10(exp 17) atoms/sq cm per sec at temperatures in the range 285 to 375 F (140 to 191 C) for time intervals between 2 and 50 minutes. Rutherford backscattering spectroscopy (RBS) was used to determine the thickness of the oxide layers formed and the ratio of the number of copper to oxygen atoms in the layers. Oxide film thicknesses ranged from 50 to 3000 A (0.005 to 0.3 microns, or equivalently, 5 x 10(exp -9) to 3 x 10(exp -7); it was determined that the primary oxide phase was Cu2O. The growth law was found to be parabolic (L(t) varies as t(exp 1/2)), in which the oxide thickness L(t) increases as the square root of the exposure time t. The analysis of the data is consistent with either of the two parabolic growth laws. (The thin-film parabolic growth law is based on the assumption that the process is diffusion controlled, with the space charge within the growing oxide layer being negligible. The thick-film parabolic growth law is also based on a diffusion controlled process, but space-charge neutrality prevails locally within very thick oxides.) In the absence of a voltage measurement across the growing oxide, a distinction between the two mechanisms cannot be made, nor can growth by the diffusion of neutral atomic oxygen be entirely ruled out. The activation energy for the reaction is on the order of 1.1 eV (1.76 x 10(exp -19) joule, or equivalently, 25.3 kcal/mole).

Fromhold, A. T.↗