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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2015

Thermochemical Ablation Analysis of the Orion Heatshield

The Orion Multi-Purpose Crew Vehicle will one day carry astronauts to the Moon and beyond, and Orion's heatshield is a critical component in ensuring their safe return to Earth. The Orion heatshield is the structural component responsible for absorbing the intense heating environment caused by re-entry to Earth's atmosphere. The heatshield is primarily composed of Avcoat, an ablative material that is consumed during the re-entry process. Ablation is primarily characterized by two processes: pyrolysis and recession. The decomposition of in-depth virgin material is known as pyrolysis. Recession occurs when the exposed surface of the heatshield reacts with the surrounding flow. The Orion heatshield design was changed from an individually filled Avcoat honeycomb to a molded block Avcoat design. The molded block Avcoat heatshield relies on an adhesive bond to keep it attached to the capsule. In some locations on the heatshield, the integrity of the adhesive bond cannot be verified. For these locations, a mechanical retention device was proposed. Avcoat ablation was modelled in CHAR and the in-depth virgin material temperatures were used in a Thermal Desktop model of the mechanical retention device. The retention device was analyzed and shown to cause a large increase in the maximum bondline temperature. In order to study the impact of individual ablation modelling parameters on the heatshield sizing process, a Monte Carlo simulation of the sizing process was proposed. The simulation will give the sensitivity of the ablation model to each of its input parameters. As part of the Monte Carlo simulation, statistical uncertainties on material properties were required for Avcoat. Several properties were difficult to acquire uncertainties for: the pyrolysis gas enthalpy, non-dimensional mass loss rate (B´c), and Arrhenius equation parameters. Variability in the elemental composition of Avcoat was used as the basis for determining the statistical uncertainty in pyrolysis gas enthalpy and B´c. A MATLAB program was developed to allow for faster, more accurate and automated computation of Arrhenius reaction parameters. These parameters are required for a material model to be used in the CHAR ablation analysis program. This MATLAB program, along with thermogravimetric analysis (TGA) data, was used to generate uncertainties on the Arrhenius parameters for Avcoat. In addition, the TGA fitting program was developed to provide Arrhenius parameters for the ablation model of the gap filler material, RTV silicone.

Sixel, William↗
NASA NTRS2000

Accelerated Aging of Lead-Free Propellant

Following higher than expected 2-NDPA depletion rates in a lead-free doublebase formulation (RPD-422), an accelerated aging study was conducted to verify the depletion rates. A test plan was prepared to compare the aging characteristics of lead-free propellant and NOSIH-AA2. The study was also designed to determine which lead-free ballistic modifiers accelerated 2-NDPA depletion. The increased depletion rate occurred in propellants containing monobasic copper salicylate. Four lead-free propellants were then formulated to improved aging characteristics over previous lead-free propellant formulations. The new formulations reduced or replaced the monobasic copper salicylate. The new formulations had improved aging characteristics. Their burn rates, however, were unacceptable for use in a 2.75 inch rocket. To compare aging characteristics, stabilizer depletion rates of RPD-422, AA2, M28, and RLC 470/6A were measured or taken from the literature. The data were fit to a kinetic model. The model contained first and zero order terms which allowed the stabilizer concentration to go to zero. In the model, only the concentration of the primary stabilizer was considered. Derivatives beyond the first nitrated or nitroso derivative of 2-NPDA were not considered. The rate constants were fit to the Arrhenius equation and extrapolated to lower temperatures. The time to complete stabilizer depletion was estimated using the kinetic model. The four propellants were compared and the RPD-422 depleted faster at 45 C than both A22 and M28. These types of predictions depend on the validity of the model and on confidence in the Arrhenius relationship holding at lower temperatures. At 45 C, the zero order portion of the model dominates the depletion rate.

Furrow, Keith W.↗
NASA NTRS1974

A flash photolysis-resonance fluorescence kinetics study of the reaction S/3P/ + OCS

Using the technique of flash photolysis-resonance fluorescence, the reaction of ground-state atomic sulfur with carbonyl sulfide has been investigated over the temperature range from 233 to 445 K. Over this temperature range, the experimental data were fitted to an Arrhenius equation of the form k sub 1 = (1.52 plus or minus 0.20) x 10 to the minus 12th power exp(-3.63 plus or minus 0.12 kcal/mol/RT) cu cm/molecule/sec. A comparison of these results with previous investigations on this reaction system is presented.

Klemm, R. B.↗
NASA NTRS1976

Absolute rate of the reaction of O/3-P/ with hydrogen sulfide over the temperature range 263 to 495 K

The technique of flash photolysis coupled with time resolved detection of O via resonance fluorescence has been used to obtain rate constants for the reaction of O(3-P) with H2S at temperatures from 263 to 495 K and at pressures in the range 10-400 torr. Under conditions where secondary reactions are avoided, the measured rate constants for the primary step obey the Arrhenius equation k = (7.24 plus or minus 1.07) x 10 to the -12th exp(-3300 plus or minus 100/1.987 T) cu cm/molecules/s. Experiments with D2S show that the reaction exhibits a primary isotope effect, in support of a hydrogen abstraction mechanism.

Whytock, D. A.↗
NASA NTRS1976

Absolute rate constants for O + NO + N2 yields NO2 + N2 from 217-500 K

Rate constants for the reaction O + NO + N2 yields NO2 + N2 from 217 to 500 K were obtained by a method combining the flash photolysis of NO with the time resolved detection of O by means of resonance fluorescence. The rate constants were found to obey the Arrhenius equation k = (15.5 plus or minus 2.0) x 10 to the -33rd exp((1160 plus or minus 70)/1.987 T) cm to the 6th/squared molecule/s, while the temperature dependence of k is described by k = 3.80 x 10 to the -27th/T to the 1.82 cm to the 6th/squared molecule/s.

Whytock, D. A.↗
NASA NTRS1977

Flash photolysis resonance fluorescence investigation of the reaction of Cl/2P/ atoms with ClONO2

Rate constants for the removal of Cl(2P) atoms by homogeneous gas phase reaction with ClONO2 were measured using the flash photolysis resonance fluorescence technique at 224, 250, and 273 K. The values obtained have been used to derive the above Arrhenius equation. The uncertainties expressed are 95% confidence limits obtained using the statistical standard deviation of the individual rate constants plus a 15% additional estimated uncertainty attributed to difficulties in chlorine nitrate concentration measurements. The results indicate that destruction of chlorine nitrate by reaction with chlorine atoms is perhaps the least important of the atmospheric reactive channels, and is at least three orders of magnitude slower than calculated photodissociation rates at all stratospheric altitudes.

Kurylo, M. J.↗
NASA NTRS1979

A flash photolysis resonance fluorescence investigation of the reaction OH + CH3CCl3 yields H2O + CH2CCl3

The absolute rate constant for the reaction OH + CH3CCl3 yields H2O + CH2CCl3 was determined by the flash photolysis resonance fluorescence method from 253 to 363K. The use of the Arrhenius equation with atmospheric observational data on methyl chloroform nearly doubles the predicted tropospheric OH reaction sink strength for the removal of atmospheric gases whose lifetimes are controlled by OH. The increased use of methyl chloroform instead of the restricted trichloroethylene focused attention to its role in stratospheric ozone depletion, producing modeling analyses to determine the amount of released methyl chloroform which reaches the stratosphere. Since the primary atmospheric loss of CH3CCl3 is considered by reaction with OH radicals, these data are used to compute an average tropospheric OH concentration and the strength of the 'global tropospheric OH reaction sink'.

Kurylo, M. J.↗
NASA NTRS1989

Differential Curing In Fiber/Resin Laminates

Modified layup schedule counteracts tendency toward delamination. Improved manufacturing process resembles conventional process, except prepregs partially cured laid on mold in sequence in degree of partial cure decreases from mold side to bag side. Degree of partial cure of each layer at time of layup selected by controlling storage and partial-curing temperatures of prepreg according to Arrhenius equation for rate of gel of resin as function of temperature and time from moment of mixing. Differential advancement of cure in layers made large enough to offset effect of advance bag-side heating in oven or autoclave. Technique helps prevent entrapment of volatile materials during manufacturing of fiber/resin laminates.

Webster, Charles N.↗
NASA NTRS1989

Contamination of liquid oxygen by pressurized gaseous nitrogen

The penetration of pressurized gaseous nitrogen (GN2) into liquid oxygen (LOX) was investigated experimentally in the 7-inch High Temperature Tunnel, the pilot tunnel for the 8-foot High Temperature Tunnel (8'HTT) at Langley Research Center. A preliminary test using a nuclear monitor revealed the extent of the liquid nitrogen (LN2) build-up at the LOX interface as a function of GN2 pressure. Then an adaptation of the differential flash vaporization technique was used to determine the binary diffusivity of the LOX-LN2 system at a temperature of 90.2 K. The measured value D equals 0.000086 sq cm/s + or - 25 percent together with two prior measurements at lower temperatures revealed an excellent fit to the Arrhenius equation, yielding a pre-exponential factor D sub 0 equals 0.0452 sq cm/s and an activation enthalpy H equals 1.08 kcal/mol. At a pressure of 1700 psi and holding time of 15 min, the penetration of LN2 into LOX (to a 1 percent contamination level) was found to be 0.9 cm, indicating but minimal impact upon 8'HTT operations.

Zuckerwar, Allan J.↗
NASA NTRS1989

Photocatalytic post-treatment in waste water reclamation systems

A photocatalytic water purification process is described which effectively oxidizes organic impurities common to reclaimed waste waters and humidity condensates to carbon dioxide at ambient temperatures. With this process, total organic carbon concentrations below 500 ppb are readily achieved. The temperature dependence of the process is well described by the Arrhenius equation and an activation energy barrier of 3.5 Kcal/mole. The posttreatment approach for waste water reclamation described here shows potential for integration with closed-loop life support systems.

Cooper, Gerald↗
NASA NTRS1992

Thermal protection materials: Thermophysical property data

This publication presents a thermophysical property survey on materials that could potentially be used for future spacecraft thermal protection systems (TPS). This includes data that was reported in the 1960's as well as more current information reported through the 1980's. An attempt was made to cite the manufacturers as well as the data source in the bibliography. This volume represents an attempt to provide in a single source a complete set of thermophysical data on a large variety of materials used in spacecraft TPS analysis. The property data is divided into two categories: ablative and reusable. The ablative materials have been compiled into twelve categories that are descriptive of the material composition. An attempt was made to define the Arrhenius equation for each material although this data may not be available for some materials. In a similar manner, char data may not be available for some of the ablative materials. The reusable materials have been divided into three basic categories: thermal protection materials (such as insulators), adhesives, and structural materials.

Williams, S. D.↗
NASA NTRS1992

Experimental dehydration of natural obsidian and estimation of DH2O at low water contents

Water diffusion experiments were carried out by dehydrating rhyolitic obsidian from Valles Caldera (New Mexico, USA) at 510-980 degrees C. The starting glass wafers contained approximately 0.114 wt% total water, lower than any glasses previously investigated for water diffusion. Weight loss due to dehydration was measured as a function of experiment duration, which permits determination of mean bulk water diffusivity, mean Dw. These diffusivities are in the range of 2.6 to 18 X 10(-14) m2/s and can be fit with the following Arrhenius equation: ln mean Dw (m2/s) = -(25.10 +/- 1.29) - (46,480 +/- 11,400) (J/mol) / RT, except for two replicate runs at 510 degrees C which give mean Dw values much lower than that defined by the above equation. When interpreted according to a model of water speciation in which molecular H2O is the diffusing species with concentration-independent diffusivity while OH units do not contribute to the transport but react to provide H2O, the data (except for the 510 degrees C data) are in agreement with extrapolation from previous results and hence extend the previous data base and provide a test of the applicability of the model to very low water contents. Mean bulk water diffusivities are about two orders of magnitude less than molecular H2O diffusivities because the fraction of molecular H2O out of total water is very small at 0.114 wt% total water and less. The 510 degrees C experimental results can be interpreted as due to slow kinetics of OH to H2O interconversion at low temperatures.

NASA Program Exobiology↗
NASA NTRS2018

Maximum Sample Temperature for Mars Sample Return: A Historical Perspective

Since the first Mars Sample Return (MSR) report published by the Jet Propulsion Laboratory (JPL) in 1974 [1], a series of panels, reports, and white papers have recognized the importance of sample temperature and offered an informed sample maximum temperature (henceforth SMT) limit for returning martian samples to Earth. The Mars Sample Handling and Requirements Panel (MSHARP, 1999) stated that "[t]he main issue in sample preservation is temperature" [2]. More recently, the Mars Exploration Program Analysis Group (MEPAG)'s "Science Priorities for Mars Sample Return" report (2008), declared that "[s]ignificant loss, particularly to biological studies, occurs if samples reach +50C for three hours", whereby "scientific objectives related to life goals could be seriously compromised" [3]. By contrast, the Mars 2020 mission has adopted a SMT of +60C as spelled out in Beaty et al., 2016 [4]. Samples will be collected and then deposited on the surface in sealed tubes for possible retrieval and return to Earth. Beaty et al. [4] calculates that the samples will experience maximum temperatures of ~+30 to +60C, depending on latitude. At present, there is no mission requirement for the measurement/data logging of sample temperature during this period. We will explore the history of martian SMTs, as they have been recorded since 1974 [1], effectively representing input across multiple generations of Mars scientists. Ten separate publications present SMTs for MSR samples [1-10]. One report [10] is for a mission concept specifically designed to exclude life detection investigations, and recommended an SMT of 50C. Another did not specify a temperature, recommending "Mars ambient temperature" [5]. Of the remaining eight, SMTs are given as: -30C [1], -20C [3], 60C [4], -73 to 41C depending on sample type [6], -40C [7], -43 to 13C depending on type [2,8], and -33C [9]. If we restrict the temperatures to samples highlighted in the Mars 2020 mission goals, i.e. organics-bearing and sedimentary rocks, then the average SMT is -28+/-39C (n=8). Applying a Dixon's Q Test at P=0.05 (two-tailed), the 60C SMT [4] fails with Q=0.602 versus Qcrit=0.526. Excluding the outlier produces an average SMT of -40+/-17C (n=7). Therefore, the average SMT expressed by the Mars science community over the past 44 years (two generations) is a sample temperature no greater than -40C. The difference in chemical reaction rates between this average SMT and Beaty et al [4] can be estimated using the Arrhenius equation. Assuming a generic chemical reaction with an activation energy of 50 kJ/mol and a pre-exponential factor invariant with temperature, this reaction will proceed 2300x faster at 60C than at -40C. To illustrate the effects of the increased reaction rate, consider 10 ppb of alanine in a Mars 2020 cache, and assume that it becomes unmeasurable if it degrades to 1 ppb, as per the Mars 2020 Organic Contamination Panel contamination limits [11]. If we illustrate the effect with an arbitrary degradation rate such that the alanine will become undetectable in ten years at -40C, then the same 10 ppb alanine degrades beyond detectability in only 38 days at 60C. Further research is required to quantify expected analyte losses in the cached samples due to thermal processing.

Fries, Marc↗
NASA NTRSDate not supplied

Predicting Thermal Response in a Li-ion Cell on a UAV Fight Profile

As the energy storage devices continue to "pack" more energy in a small space, any damage, battery component failure, manufacturing defect, or electrically abusing the battery can lead to catastrophic thermal runaway events. A catastrophic thermal event in a cell leads to high temperature, in some instances spewing of battery materials due to gas development from side reactions initiated due to high internal temperatures. Also, a thermal runaway event can propagate from a single "failed" cell to the pack in a battery pack, leading to a more significant event. Mitigating a thermal runaway event is important in the commercial and automotive sectors. However, preventing such events in an electric aircraft (or air taxis) is paramount due to the lack of alternatives in the event of a failure. Battery prognostics algorithms allow the prediction of state-of-charge (SOC) and end-of-life (EOL) of a Li-ion battery in a UAV (unmanned air vehicle) [1]. For this presentation, we will extend this two-level battery predictive algorithm to predict SOC, EOL, and estimated maximum temperature during a simulated flight. The model is extended by integrating a lumped physics-driven thermal model for high current densities [2]. The parameters used to control SOC and EOL are maximum storable charge, time constant for Li-ion diffusivity in the carbon particles, and internal cell resistance. Cycling leads to an increase in the heat generated by an aged Li-ion cell with a LiyCoO2 (LCO) cathode and a LixC6 (MCMB) anode. The aging of a cell leads to increase in SEI layer thickness, the diffusion time for the lithium ions inside the electrodes, and the local reaction rates, in addition to the thermodynamic abuse caused by fixed cycling voltages controlled by a Battery Management System. As the battery ages, the cell resistance increases, while the onset temperature of the thermal runaway decreases (depends on the cell chemistry and cell abuse history). Any large deviation of the cell temperature from the estimated (expected) value can identify a faulty cell. Since SEI decomposition has the lowest onset temperature in the series of reactions leading to thermal runaway, the model considers the self-heating rate of the SEI decomposition as onset temperature (similar to Ref. [3]). The parameters in the Arrhenius equation for the SEI heating rate depend on the number of cycles, the cell's operating temperature, and the cell's abuse history [4,5]. Coupling the electrochemical, thermal, and aging model allow the prognostic algorithm to estimate a typical cell voltage and temperature as a function of age (cycling and calendar), whose departure from measured values from the BMS is used to identify a safety event. In addition, we will present the results from two simulated flight scenarios for a UAV: typical and extreme, since the power requirements vary significantly during take-off, landing, and changing altitudes, while the power requirements remain low during the cruise. For this presentation, the power requirement for a battery pack in a UAV is scaled to a single cell. This cell is cycled through a simulated profile, and the data is collected and used to predict a safety event.

Li-ion↗
NASA NTRS1988

Numerical modeling of chemical vapor deposition (CVD) in a horizontal reactor

In the present numerical prediction of the deposition rate of silicon from silane in a CVD process, the conservation equations for mass, momentum, energy, and chemical species are solved on a staggered grid using the SIMPLE algorithm, while the rate of chemical reactions in the gas phase and on the susceptor surface is obtained from an Arrhenius rate equation. Predicted deposition rates as a function of position along the susceptor with and without the gas phase chemical reaction are compared with the available experimental and numerical data; agreement is excellent except at the leading edge of the susceptor, where the deposition rate is overpredicted.

Sheikholeslami, M. Z.↗
NASA NTRS1993

Modeling of outgassing and matrix decomposition in carbon-phenolic composites

A new release rate equation to model the phase change of water to steam in composite materials was derived from the theory of molecular diffusion and equilibrium moisture concentration. The new model is dependent on internal pressure, the microstructure of the voids and channels in the composite materials, and the diffusion properties of the matrix material. Hence, it is more fundamental and accurate than the empirical Arrhenius rate equation currently in use. The model was mathematically formalized and integrated into the thermostructural analysis code CHAR. Parametric studies on variation of several parameters have been done. Comparisons to Arrhenius and straight-line models show that the new model produces physically realistic results under all conditions.

Mcmanus, Hugh L.↗
NASA NTRS2019

Permeation Rate Equations for Hydrogen and Deuterium in a Palladium-Silver Alloy

Mass transfer of a gas through a selective, solid membrane is an effective method for separation of desired species. This selective permeability is evident in the flow of hydrogen and the isotope deuterium through palladium-silver metal alloy media. In this study, based upon Sieverts’s law and the Arrhenius diffusion equation, an empirical correlation was developed to determine the steady-state permeation rate R, dependence on media temperature T, gas supply pressure p(sub S), and gas backpressure p(sub B) on the lower pressure side. Because of an extensive range of experimental conditions and complete reporting of raw data, the research by Ackerman and Koskinas was used as a source for data allowing empirical equation fitting. Unfortunately, those authors reported best-fit equations that poorly represented their own results. To improve the modeling of the original data and demonstrate the quality of the measurements, the current study develops improved hydrogen and deuterium permeation rate equations: P = 4.22×10(exp −6) A[exp(−704/T)](sq. root p(sub S) − sq. root p(sub B))/t for hydrogen P = 2.12×10(exp −6) A[exp(−468/T )](sq. root p(sub S) − sq. root p(sub B))/t for deuterium for values of cross-sectional area A (sq.cm), medium thickness t (cm), pressure p (psia), and temperature T (Kelvin), giving a permeation rate in mole/minute. These equations model permeation rate data more closely than do several other existing literature sources.

Smith, Phillip J.↗