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At least 379 records · Page 21

Laser-Induced Fluorescence Measurements of Energetic Ions in a 100-A LaB6 Hollow Cathode

Increasingly long-duration space missions require a better understanding of the failure mechanisms of hollow cathodes to enable prediction of lifetime. Energetic ions have been measured in the plume of hollow cathodes but the energies are higher than can be explained classically. One of the mechanisms that appears to be contributing to the ion heating is ion acoustic turbulence (IAT), which has been investigated with plasma probes recently at JPL. In this work the ion velocity distribution has been measured using laser-induced fluorescence (LIF) at several high-current operating conditions on the centerline of a 100 A class hollow cathode at JPL. A retarding potential analyzer was (RPA) was used to measure the ion energy profile in the far plume and a Langmuir probe was used to measure electron temperature and plasma potential fluctuations. RPA energies are shown to correlate with the values measured by LIF. The ion temperature is shown to increase with distance downstream of the cathode. A parametric study of the ion heating as a function of discharge current and cathode flow rate was performed. It was found that for increasing current the ion temperature evolution did not vary even though the wave IAT wave energy increased. The effect of flow rate was more pronounced, with higher values reducing both ion temperature and wave energy linearly. These results indicate that IAT is at least partially responsible for energetic ion production in the hollow cathode plume.

Dodson, Christopher A.↗

Thermal system and environmental testing of the Mars Helicopter

The Mars Helicopter will be a technology demonstration conducted during the Mars 2020 mission. The primary mission objective is to achieve several 90-second flights demonstrating the feasibility of heavier than air flight on Mars and capture visible light images via forward and nadir mounted cameras. These flights could possibly provide reconnaissance data for sampling site selection for other Mars surface missions. A solar array and batteries for flight operations, imaging, communications, and survival heating power the Helicopter. The thermal design is driven by minimizing survival heater energy while maintaining compliance with allowable flight temperatures in a variable thermal environment. Due to the small size of the Helicopter and its complex geometries, along with the fact that it operates with very low power and small margins in the extreme Mars environment, additional care had to be paid while planning thermal tests and designing the thermal system. The first section of the paper describes the evolution of the thermal system of the Mars Helicopter. After the first thermal vacuum test of the engineering model, the thermal team has conducted a partial effect analysis on the thermal design components that had a major impact on the system performance. Several design choices derived by analysis and test have been made to meet the energy allocation and the temperature requirements. These changes included increased gas gaps to reduce gas conduction, low emissivity coatings for internal components, blanket implementation, optimization of wire routing and fine-tuning of surface operations to optimize waste heat recovery. The second part of the paper describes the flight model thermal vacuum test and the subsequent thermal model correlation necessary to confirm the fidelity of the analysis results.

Pauken, Michael↗

Left ventricular endocardial surface detection based on real-time 3D echocardiographic data

OBJECTIVE: A new computerized semi-automatic method for left ventricular (LV) chamber segmentation is presented. METHODS: The LV is imaged by real-time three-dimensional echocardiography (RT3DE). The surface detection model, based on level set techniques, is applied to RT3DE data for image analysis. The modified level set partial differential equation we use is solved by applying numerical methods for conservation laws. The initial conditions are manually established on some slices of the entire volume. The solution obtained for each slice is a contour line corresponding with the boundary between LV cavity and LV endocardium. RESULTS: The mathematical model has been applied to sequences of frames of human hearts (volume range: 34-109 ml) imaged by 2D and reconstructed off-line and RT3DE data. Volume estimation obtained by this new semi-automatic method shows an excellent correlation with those obtained by manual tracing (r = 0.992). Dynamic change of LV volume during the cardiac cycle is also obtained. CONCLUSION: The volume estimation method is accurate; edge based segmentation, image completion and volume reconstruction can be accomplished. The visualization technique also allows to navigate into the reconstructed volume and to display any section of the volume.

Non-NASA Center↗

The Multi-Stage History of Mt. Sharp

The Curiosity rover is exploring Gale crater and Mt. Sharp, Gale's 5‐km high central mound. We are investigating the history of alteration and erosion of Mt. Sharp using orbital imagery, spectroscopy and rover observations. Our results suggest a significant time gap between emplacement of the upper and lower sections of the mound. Crater counts show that the lower mound was formed soon after Gale itself, and that it contains distinct units ranging in altitude from approximately ‐4,500 to ‐1,800 m. Spectral data suggest that many units contain phyllosilicates. We found that these clay‐bearing rocks occur in distinct layers concentrated below ‐2,900 m. Parts of the lower mound exhibit a transition from clays to sulfates with increasing altitude. The lower mound shows evidence of flowing water, including canyons and inverted channels. Wind erosion produced km‐scale yardangs and scalloped cliffs. Our mapping shows that many yardangs in the lower mound are clay‐bearing, with a predominant orientation of around N‐S. Curiosity's ground‐level images show myriad fine‐scale, mainly horizontal layers in the lower mound. The rover has found stream beds and conglomerates, indicating that water once flowed on the crater floor. Drilling near the deepest point in Gale produced abundant clay, providing additional evidence of aqueous alteration. Upper mound units range in altitude from ‐2,100 m to +500 m, and mantle the lower mound above an angular unconformity. Most upper mound units are composed of layers. The formation age of the upper mound is unknown, since few craters are preserved. Clay‐bearing layers are detectable in several locations, mainly at altitudes near ‐2,000 m. There is no evidence of water flow, but wind erosion has scalloped the surfaces and edges of layers, and fine‐scale yardangs are common. Correlations between yardangs and clay spectra are apparent only in the lowermost units of the upper mound. Yardang orientations vary, and include N‐S, NW‐SE, and NE‐SW. Upper mound units resemble the planet‐wide Medusae Fossae formation, dated as Hesperian and argued to be composed of ignimbrites. Medusae Fossae layers are easily eroded by wind, and our mapping demonstrates their resemblance to upper mound fine‐scale yardangs. The history of Mt. Sharp started with deposition and lithification of sediments shortly after crater formation. Some lower mound layers were partially altered to clays and sulfates, and water formed streams and canyons. Wind erosion of the lower mound produced large‐scale yardangs, particularly in clay‐rich layers, oriented generally N‐S. Upper mound units were emplaced following a considerable period of wind erosion. The absence of water flow on the upper mound suggests that these units were emplaced after atmospheric loss rendered water unstable at the surface. The shift in dominant wind direction, as indicated by yardang orientations, also argues for a time gap between erosion of the lower and upper mound. These observations are consistent with upper mound units being related to the Hesperian Medusae Fossae formation. During 2014 Curiosity is expected to reach the foot of Mt. Sharp and ascend through the clay‐rich layers, into the sulfate‐rich layers, and possibly past the interface with the upper mound. This will be a unique opportunity to field check geologic models on the surface of Mars.

Allen, C.↗

Hypovolemia in syncope and orthostatic intolerance role of the renin-angiotensin system

PURPOSE: Orthostatic intolerance is the cause of significant disability in otherwise normal patients. Orthostatic tachycardia is usually the dominant hemodynamic abnormality, but symptoms may include dizziness, visual changes, discomfort in the head or neck, poor concentration, fatigue, palpitations, tremulousness, anxiety and, in some cases, syncope. It is the most common disorder of blood pressure regulation after essential hypertension. There is a predilection for younger rather than older adults and for women more than men. Its cause is unknown; partial sympathetic denervation or hypovolemia has been proposed. METHODS AND MATERIALS: We tested the hypothesis that reduced plasma renin activity, perhaps from defects in sympathetic innervation of the kidney, could underlie a hypovolemia, giving rise to these clinical symptoms. Sixteen patients (14 female, 2 male) ranging in age from 16 to 44 years were studied. Patients were enrolled in the study if they had orthostatic intolerance, together with a raised upright plasma norepinephrine (> or = 600 pg/mL). Patients underwent a battery of autonomic tests and biochemical determinations. RESULTS: There was a strong positive correlation between the blood volume and plasma renin activity (r = 0.84, P = 0.001). The tachycardic response to upright posture correlated with the severity of the hypovolemia. There was also a correlation between the plasma renin activity measured in these patients and their concomitant plasma aldosterone level. CONCLUSIONS: Hypovolemia occurs commonly in orthostatic intolerance. It is accompanied by an inappropriately low level of plasma renin activity. The degree of abnormality of blood volume correlates closely with the degree of abnormality in plasma renin activity. Taken together, these observations suggest that reduced plasma renin activity may be an important pathophysiologic component of the syndrome of orthostatic intolerance.

Non-NASA Center↗

Ares I-X Flight Evaluation Tasks in Support of Ares I Development

NASA s Constellation Program successfully launched the Ares I-X Flight Test Vehicle on October 28, 2009. The Ares I-X flight was a development flight test that offered a unique opportunity for early engineering data to impact the design and development of the Ares I crew launch vehicle. As the primary customer for flight data from the Ares I-X mission, the Ares Projects Office established a set of 33 flight evaluation tasks to correlate fight results with prospective design assumptions and models. Included within these tasks were direct comparisons of flight data with pre-flight predictions and post-flight assessments utilizing models and modeling techniques being applied to design and develop Ares I. A discussion of the similarities and differences in those comparisons and the need for discipline-level model updates based upon those comparisons form the substance of this paper. The benefits of development flight testing were made evident by implementing these tasks that used Ares I-X data to partially validate tools and methodologies in technical disciplines that will ultimately influence the design and development of Ares I and future launch vehicles. The areas in which partial validation from the flight test was most significant included flight control system algorithms to predict liftoff clearance, ascent, and stage separation; structural models from rollout to separation; thermal models that have been updated based on these data; pyroshock attenuation; and the ability to predict complex flow fields during time-varying conditions including plume interactions.

Huebner, Lawrence D.↗

Development of a Composite Material Aerodynamic Demise Model for the Object Reentry Survival Analysis Tool (ORSAT)

The reentry demise of fiber-reinforced polymer (FRP) composites is an increasing concern for modern spacecraft at end of life. Unlike traditional materials such as metals, shredding of the material by aerodynamic forces appears to be a major component of the reentry demise mechanism. This paper will describe a new mechanical, strength-based, material demise model for the Object Reentry Survival Analysis Tool (ORSAT) Version 7.1. The model is based on laboratory in-situ and residual strength tests of several FRP materials performed during the NASA Orbital Debris Program Office’s Phase II Composite Material Demise test campaign. To test the residual strength of partially charred FRP materials, the authors tested 107 rectangular shaped samples of different thicknesses that were previously exposed to high-enthalpy flow at the University of Texas at Austin’s Inductively Coupled Plasma Torch facility. Tests were performed under normal atmospheric conditions at NASA Johnson Space Center’s Experimental Impact Laboratory using a Chatillon TCD1000 tensile test machine configured with a three-point bending jig. Mean fracture load, residual strength, delamination, and flexural modulus were measured for each test. An engineering model of aeromechanical demise for each material was developed by correlating the measured residual strength of the samples with the duration and magnitude of the applied heat flux and the mass loss and char progression. This model has been implemented in ORSAT 7.1 for the built-in, charring carbon fiber/epoxy and charring glass fiber/epoxy material models. The new model was verified by calculating the demise of hundreds of FRP composite fragments of various shapes and sizes and checking the calculations for consistency, with specific focus on material characterization in one-dimension. Further tests are planned in hypersonic flow facilities to validate the assumptions used in the model.

Priscilla A. Mendoza↗

Development of a Composite Material Aerodynamic Demise Model for the Object Reentry Survival Analysis Tool (ORSAT)

The reentry demise of fiber-reinforced polymer (FRP) composites is an increasing concern for modern spacecraft at end of life. Unlike traditional materials such as metals, shredding of the material by aerodynamic forces appears to be a major component of the reentry demise mechanism. This paper will describe a new mechanical, strength-based, material demise model for the Object Reentry Survival Analysis Tool (ORSAT) Version 7.1. The model is based on laboratory in-situ and residual strength tests of several FRP materials performed during the NASA Orbital Debris Program Office’s Phase II Composite Material Demise test campaign. To test the residual strength of partially charred FRP materials, the authors tested 107 rectangular shaped samples of different thicknesses that were previously exposed to high-enthalpy flow at the University of Texas at Austin’s Inductively Coupled Plasma Torch facility. Tests were performed under normal atmospheric conditions at NASA Johnson Space Center’s Experimental Impact Laboratory using a Chatillon TCD1000 tensile test machine configured with a three-point bending jig. Mean fracture load, residual strength, delamination, and flexural modulus were measured for each test. An engineering model of aeromechanical demise for each material was developed by correlating the measured residual strength of the samples with the duration and magnitude of the applied heat flux and the mass loss and char progression. This model has been implemented in ORSAT 7.1 for the built-in, charring carbon fiber/epoxy and charring glass fiber/epoxy material models. The new model was verified by calculating the demise of hundreds of FRP composite fragments of various shapes and sizes and checking the calculations for consistency, with specific focus on material characterization in one-dimension. Further tests are planned in hypersonic flow facilities to validate the assumptions used in the model.

Priscilla A. Mendoza↗

Correlation between Mechanical Behavior and Actuator-type Performance of Ni-Ti-Pd High-temperature Shape Memory Alloys

High-temperature shape memory alloys in the NiTiPd system are being investigated as lower cost alternatives to NiTiPt alloys for use in compact solid-state actuators for the aerospace, automotive, and power generation industries. A range of ternary NiTiPd alloys containing 15 to 46 at.% Pd has been processed and actuator mimicking tests (thermal cycling under load) were used to measure transformation temperatures, work behavior, and dimensional stability. With increasing Pd content, the work output of the material decreased, while the amount of permanent strain resulting from each load-biased thermal cycle increased. Monotonic isothermal tension testing of the high-temperature austenite and low temperature martensite phases was used to partially explain these behaviors, where a mismatch in yield strength between the austenite and martensite phases was observed at high Pd levels. Moreover, to further understand the source of the permanent strain at lower Pd levels, strain recovery tests were conducted to determine the onset of plastic deformation in the martensite phase. Consequently, the work behavior and dimensional stability during thermal cycling under load of the various NiTiPd alloys is discussed in relation to the deformation behavior of the materials as revealed by the strain recovery and monotonic tension tests.

Bigelow, Glen S.↗

Reliability enhancement of Navier-Stokes codes through convergence acceleration

Methods for enhancing the reliability of Navier-Stokes computer codes through improving convergence characteristics are presented. The improving of these characteristics decreases the likelihood of code unreliability and user interventions in a design environment. The problem referred to as a 'stiffness' in the governing equations for propulsion-related flowfields is investigated, particularly in regard to common sources of equation stiffness that lead to convergence degradation of CFD algorithms. Von Neumann stability theory is employed as a tool to study the convergence difficulties involved. Based on the stability results, improved algorithms are devised to ensure efficient convergence in different situations. A number of test cases are considered to confirm a correlation between stability theory and numerical convergence. The examples of turbulent and reacting flow are presented, and a generalized form of the preconditioning matrix is derived to handle these problems, i.e., the problems involving additional differential equations for describing the transport of turbulent kinetic energy, dissipation rate and chemical species. Algorithms for unsteady computations are considered. The extension of the preconditioning techniques and algorithms derived for Navier-Stokes computations to three-dimensional flow problems is discussed. New methods to accelerate the convergence of iterative schemes for the numerical integration of systems of partial differential equtions are developed, with a special emphasis on the acceleration of convergence on highly clustered grids.

Merkle, Charles L.↗

Numerical Modeling of No Vent Filling of a Cryogenic Tank

This paper presents a multi-node finite volume model of the chilling and filling of a cryogenic tank using the Generalized Fluid System Simulation Program (GFSSP), a general purpose flow network code. Vented Chill and No Vent Fill (VCNVF) tests were conducted at Marshall Space Flight Center where a flight-like tank was filled with liquid nitrogen from a supply tank. In the VCNVF tests, the tank was partially chilled while the vent valve was open. After the partial chilling, the vent valve was closed and the tank was filled without any venting. An integrated numerical model of the test set up was developed. The model included the transfer line from the supply tank, the target tank with the spray nozzle and solid walls, and the discharge line with the vent valve. The tank was discretized into multiple fluid nodes and branches to represent the ullage and liquid nitrogen and multiple solid nodes to represent the tank wall and structure. The heat transfer between solid to fluid was calculated from pool boiling correlations which include film, transition, and nucleate boiling, as well as natural convection during pre- and post-boiling. The model also accounts for the condensation of vapor in the tank when it comes in contact with the liquid spray. The predicted pressure, resident mass, wall and ullage temperature in the tank were compared with the test data.

Alok Majumdar↗

Numerical Modeling of No Vent Filling of a Cryogenic Tank

This paper presents a multi-node finite volume model of the chilling and filling of a cryogenic tank using the Generalized Fluid System Simulation Program (GFSSP), a general purpose flow network code. Vented Chill and No Vent Fill (VCNVF) tests were conducted at Marshall Space Flight Center where a flight-like tank was filled with liquid nitrogen from a supply tank. In the VCNVF tests, the tank was partially chilled while the vent valve was open. After the partial chilling, the vent valve was closed and the tank was filled without any venting. An integrated numerical model of the test set up was developed. The model included the transfer line from the supply tank, the target tank with the spray nozzle and solid walls, and the discharge line with the vent valve. The tank was discretized into multiple fluid nodes and branches to represent the ullage and liquid nitrogen and multiple solid nodes to represent the tank wall and structure. The heat transfer between solid to fluid was calculated from pool boiling correlations which include film, transition, and nucleate boiling, as well as natural convection during pre- and post-boiling. The model also accounts for the condensation of vapor in the tank when it comes in contact with the liquid spray. The predicted pressure, resident mass, wall and ullage temperature in the tank were compared with the test data.

Alok Majumdar↗

Perceiving the coherent movements of spatially-separated features

When a partially-occluded object is represented in an image, it is defined by a set of spatially-separated features that may be registered at different spatial scales. To understand the image, human vision must organize these fragmented optical features into common and distinct object surfaces. Although the common fate of moving features often is considered a primary source of reliable information for image segmentation, little is known of the visual system's capacity to discriminate the coherent relative movements of spatially-separated features. In a series of experiments, observers viewed elements whose movements were correlated (direction and magnitude) or were uncorrelated. Our results indicate that observers can discriminate the two types of movement about as well as they can detect any movement at all. Moreover, the ability to perceive coherent movements is maintained under a variety of conditions including differences in the elements' spatial frequency content, spatial position and contrast, and temporal phase shifts between the spatially-correlated displacements. These results suggest that coherent relative motion may be a fundamental source of information exploited by vision, despite considerable variability in the spatial and temporal characteristics of the individual features.

Mowafy, Lyn↗

Surface settling in partially filled containers upon step reduction in gravity

A large literature exists concerning the equilibrium configurations of free liquid/gas surfaces in reduced gravity environments. Such conditions generally yield surfaces of constant curvature meeting the container wall at a particular (contact) angle. The time required to reach and stabilize about this configuration is less studied for the case of sudden changes in gravity level, e.g. from normal- to low-gravity, as can occur in many drop tower experiments. The particular interest here was to determine the total reorientation time for such surfaces in cylinders (mainly), as a function primarily of contact angle and kinematic viscosity, in order to aid in the development of drop tower experiment design. A large parametric range of tests were performed and, based on an accompanying scale analysis, the complete data set was correlated. The results of other investigations are included for comparison.

Weislogel, Marl M.↗

Early Petrologic Processes on the Ureilite Parent Body

We present a petrographic and petrologic analysis of 21 olivine-pigeonite ureilites, along with new experimental results on melt compositions predicted to be in equilibrium with ureilite compositions. We conclude that these ureilites are the residues of a partial melting/smelting event. Textural evidence preserved in olivine and pigeonite record the extent of primary smelting. In pigeonite cores, we observe fine trains of iron metal inclusions that formed by the reduction of olivine to pigeonite and metal during primary smelting. Olivine cores lack metal inclusions but the outer grain boundaries are variably reduced by a late-stage reduction event. The modal proportion of pigeonite and percentage of olivine affected by late stage reduction are inversely related and provide an estimation of the degree of primary smelting during ureilite petrogenesis. In our sample suite, this correlation holds for 16 of the 21 samples examined. Olivine-pigeonite-liquid phase equilibrium constraints are used to obtain temperature estimates for the ureilite samples examined. Inferred smelting temperatures range from approximately 1150 C to just over 1300 C and span the range of estimates published for ureilites containing two or more pyroxenes. Temperature is also positively correlated with modal percent pigeonite. Smelting temperature is inversely correlated with smelting depth--the hottest olivine-pigeonite ureilites coming from the shallowest depth in the ureilite parent body. The highest temperature samples also have oxygen isotopic signatures that fall toward the refractory inclusion-rich end of the carbonaceous chondrite-anhydrous mineral (CCAM) slope 1 mixing line. These temperature-depth variations in the ureilite parent body could have been created by a heterogeneous distribution of heat producing elements, which would indicate that isotopic heterogeneities existed in the material from which the ureilite parent body was assembled.

Singletary, S. J.↗

Water Contents of the Mantle Beneath the Rio Grande Rift: FTIR Analysis of Kilbourne Hole Peridotite Xenoliths

Although nominally anhydrous mantle minerals contain only trace amounts of water, they are the main reservoir of water in the mantle. Added up at the scale of the Earth's mantle, these trace amounts of water represent oceans worth in mass]. Mantle xenoliths from Kilbourne Hole in southern New Mexico are ideal to study mantle water distribution in a rift tectonic setting as they come from a recently‐erupted maar in the middle of the Rio Grande Rift. Eleven lherzolites, one harzburgite, and one dunite are being analyzed for water contents by FTIR. The xenoliths will also be analyzed for major and trace element composition, Fe3+/Summation (Fe) ratios, and characterized petrologically. Olivines exhibit variable water contents with less water at the rims compared to the cores. This is probably due to H loss during decompression and xenolith transport by the host magma. Mantle water contents appear to have been primarily preserved in the core of the olivines, based on diffusion modeling of the typically plateau-shaped water content profiles across these grains. Water concentrations are in equilibrium between clino- and orthopyroxene, but olivine concentrations are typically not in equilibrium with those of either pyroxene. Lherzolites analyzed so far have water contents of 2‐12 ppm H2O in olivines, 125‐165 ppm H2O in orthopyroxenes, and 328‐447 ppm H2O in clinopyroxenes. These water contents are similar to, but with a narrower range, than those for the respective minerals in other continental peridotite xenoliths. The lherzolites have bulk-rock (BR) Al2O3 contents that range between 3.17 and 3.78 wt%, indicating similar degrees of partial melting, which could explain the narrow range of their pyroxene water contents. Primitive mantle normalized rare earth element (REE) profiles of the bulk lherzolites vary from light REE depleted to flat, with no significant differences between, nor relation to, their mineral water contents. Consequently, the metasomatic agents that enriched LREEs in these lherzolites were most likely water-poor. The harzburgite and the dunite have lower weight percent Al2O3 compared to the lherzolites (2.11% and 0.34% respectively) indicating higher degrees of melting. Their olivine water contents, however, are similar to those of the lherzolites. Moreover, no correlations are observed between pyroxene water contents and indices of melting or metasomatism between the lherzolite group, the harzburgite, and the dunite, although the latter has the lowest pyroxene water contents. More samples will be analyzed to determine if the water contents are controlled by melting, metasomatism, or a combination of the two in the Kilbourne Hole mantle.

Schaffer, Lillian A.↗

Ultrasonic and mechanical characterizations of fatigue states of graphite epoxy composite laminates

Results of an exploration of the relationship between ultrasonic attenuation and fatigue survivability of graphite fiber epoxy composites fabricated under different cure conditions are reported. A total of 9 27 x 40 cm eight-ply graphite epoxy laminated specimens were formed, and fatigue tests were run on five partial samples at 73.5 N varying at 30 Hz, with tests ending at a 1.27 cm deflection. A pulsed oscillator generated sinusoidal waves and transducers recorded the passage of the ultrasonic waves for display on oscilloscopes. Cure pressures ranged from 0.52-0.85 MPa and cure temperatures were in the 150-200 C interval. Ultrasonic through-transmission at 4 MHz was performed prior to and during fatigue testing. The minimum void volume fraction occurred at 175 C and 0.86 MPa. The flexural stiffness decreased with the number of fatigue cycles past 10,000, when the attenuation also increased. Correlations were found between the 4.0 MHz signal attenuation and the void volume fraction, and between the number of fatigue cycles to failure and the 4.0 MHz signal attenuation.

Williams, J. H., Jr.↗

Temperature-Dependent Rate Constants and Substituent Effects for the Reactions of Hydroxyl Radicals With Three Partially Fluorinated Ethers

Rate constants and temperature dependencies for the reactions of OH with CF3OCH3 (HFOC-143a), CF2HOCF2H (HFOC-134), and CF3OCF2H (HFOC-125) were studied using a relative rate technique in the temperature range 298-393 K. The following absolute rate constants were derived: HFOC-143a, 1.9E-12 exp(-1555/T); HFOC-134, 1.9E-12 exp(-2006/T); HFOC-125, 4.7E-13 exp(-2095/T). Units are cm(exp 3)molecule(exp -1) s(exp -1). Substituent effects on OH abstraction rate constants are discussed, and it is shown that the CF3O group has an effect on the OH rate constants similar to that of a fluorine atom. The effects are related to changes in the C-H bond energies of the reactants (and thereby the activation energies) rather than changes in the preexponential factors. On the basis of a correlation of rate constants with bond energies, the respective D(C-H) bond strengths in the three ethers are found to be 102, 104, and 106 kcal/mol, with an uncertainty of about 1 kcal/mol.

Hsu, K.-J.↗