Engineering topics

Jacobson, Nathan S.

Publications and source records attributed to Jacobson, Nathan S..

At least 19 records

NASA NTRS2020

Thermodynamic Measurements Using the Knudsen Cell Technique

The Knudsen cell technique has been used for over a century and is a valuable tool for measurement of vapor pressures and thermodynamic properties. It is based on a small enclosure (~1 cm long x 1 cm diameter) in which a condensed phase/vapor equilibria can be established. A small (<1 mm) orifice on the cell allows sampling of the vapor via a variety of techniques including weight loss, torsion effusion, target collection, and mass spectrometry. Many excellent measurements based on these methods have been reported. However in order to obtain reliable measurements, a variety of factors must be considered. They include proper cell material selection, accurate and uniform temperature control and measurement, and proper sampling of the vapor. Each of these factors are discussed in detail in this chapter. Typically these studies are conducted at high temperatures and it is a challenge to select an inert container material. Recommended materials are discussed and in some cases the container may be used as part of the system under study. Temperature control and measurement is perhaps the most important issue. In most systems, the furnace must be compact yet there can be no temperature gradient in the cell. Temperatures are measured with either a thermocouple or pyrometer and the relative advantages of each are discussed. Sampling method considerations depend on the particular technique. It is essential that all of the vapor or a representative portion of the vapor be sampled. The distribution of the effusate from a Knudsen cell is discussed and sampling positions discussed. Mass spectrometry is often used to study the effusing vapor and the relations between ion current and vapor pressure are discussed.

mass spectrometry↗

NASA NTRS2018

Corrigendum to "Mass Spectrometric Measurements of the Silica Activity in the Yb2O3-SiO2 System and Implications to Assess the Degradation of Silicate-Based Coatings in Combustion Environments"

The authors regret that errors appeared in the above manuscript.The corrections that need to be made are highlighted in yellow in the thermodynamic cycle of Table 2. The enthalpies in reactions 2, 5 and 6 are negative. Now that the enthalpies in reactions 2, 5 and 6 are negative, the correct enthalpy of formation of Yb2SiO5 is 2774 11 kJ mol-1. Also, the correct element in the formula Y2SiO5 on the right side of equation 2 is Yb instead Y.

Costa, Gustavo↗

NASA NTRS2017

Chemical and Microstructural Changes in Metallic and Ceramic Materials Exposed to Venusian Surface Conditions

The chemical and microstructural behavior of steels (304, 310, 316, and 1018), nickel-based alloys (beta-NiAl, G30, and 625), gold, coatings (4YSZ, SilcoNert(TradeMark) 1040 (SilcoTek Co.), Dursan(TradeMark) (SilcoTek Co.), and porcelain), and bulk ceramics (alpha-Al2O3, fused quartz, beta-SiC, and alpha-Si3N4) were probed after exposure to supercritical fluid with temperature, pressure, and composition mimicking the Venus lower atmosphere. Exposures were carried out in the Glenn Extreme Environments Rig (GEER) chamber with the Venusian gas mixture (96.5% CO2, 3.5% N2, 30 ppm H2O, 150 ppm SO2, 28 ppm CO, 15 ppm OCS, 3 ppm H2S, 0.5 ppm HCl, and 5 ppb HF) at 92 bar (1330 psi) and 467 C (873 F) for durations of 10 and 42 days. An additional 21-day exposure was done to stainless steel uncoated and coated with SilcoNert(TradeMark) and Dursan(TradeMark). Samples were characterized before and after the experiment by gravimetric analysis, X-ray diffraction, X-ray photoelectron and Auger electron spectroscopies, and cross section electron microscopy analysis. All steels exposed for 10 and 42 days formed double-layered scales consisting mainly of metal (Cr, Fe, Ni) oxides and sulfides showing different chemistry, microstructure, and crystalline phases. The alloys G30 and 625 formed double-layered scales consisting mainly of nickel sulfides. After 10 days, the beta-NiAl exhibited no detectable scale, suggesting only a very thin film was formed. The 304 and 316 stainless steels coated with 4YSZ that were exposed for 10 and 42 days exhibited no significant oxidation. Steel 1018 coated with 4YSZ exhibited a corrosion scale of iron and/or chromium oxide formed at the base of the alloy. The 304 steel coated with porcelain did not exhibit corrosion, although the coating exhibited recession. SilcoNert(TradeMark) exposed for 10 and 42 days exhibited recession, although no oxidation was found to occur at the base of the alloy. Stainless steel 316 coated with Dursan(TradeMark)  exhibited corrosion at the base of the alloy. All ceramics tested showed no clear evidence of reaction. The weight-gain-per-area performance of the materials exposed in the GEER for 10 and 42 days are reported from the lowest to the highest weight gain per area as follows: gold did not exhibit any weight change; nickel-based alloys: beta- NiAl < G30 < 625; steels: 304 < 310 < 316 < 1018; ceramics: considering the experimental uncertainties, no weight change was observed for all ceramics of this work (alpha-Al2O3, Si3N4, SiC, and amorphous SiO2).

Costa, Gustavo C. C.↗

NASA NTRS2017

Water Vapor Corrosion in EBC Constituent Materials

Environmental Barrier Coating (EBC) materials are sought after to protect ceramic matrix composites (CMC) in high temperature turbine engines. CMCs are particularly susceptible to degradation from oxidation, Ca-Al-Mg-Silicate (CMAS), and water vapor during high temperature operation which necessitates the use of EBCs. However, the work presented here focuses on water vapor induced recession in EBC constituent materials. For example, in the presence of water vapor, silica will react to form Si(OH)4 (g) which will eventually corrode the material away. To investigate the recession rate in EBC constituent materials under high temperature water vapor conditions, thermal gravimetric analysis (TGA) is employed. The degradation process can then be modeled through a simple boundary layer expression. Ultimately, comparisons are made between various single- and poly-crystalline materials (e.g. TiO2, SiO2) against those found in literature.

coating↗

NASA NTRS2017

Thermodynamics of iron-aluminum alloys at 1573 K

The activities of iron (Fe) and aluminum (Al) were measured in Fe-Al alloys at 1573 K using the ion-current-ratio technique in a high-temperature Knudsen cell mass spectrometer. The Fe-Al solutions exhibited negative deviations from ideality over the entire composition range. The activity coefficientsγ Fe, andγ A1 are given by the following equations as a function of mole fraction (x Fe,x Al): 0<χA1<0.4 ln(γ(Fe))=−4.511(±0.008)χ^(2)(A1) ln(γ(A1))=−4.462(±0.029)χ^(2)(Fe) +0.325(±0.013) 0.6<χ(A1)<1.0 ln(γ(Fe))=−4.065(±0.006)χ^(2)(A1)+0.099(±0.003) ln(γ(A1))=−4.092(±0.026)χ^(2)(Fe)+0.002(±0.001) The results showed good agreement with those obtained from previous investigations at other temperatures by extrapolation of the activity data to 1573 K.

Jacobson, Nathan S.↗

NASA NTRS2016

Monte Carlo Simulation of a Knudsen Effusion Mass Spectrometer Sampling System

Knudsen flow is easily simulated with a Monte Carlo method. In this study we develop a Visual Basic for Excel (VBA) code to simulate the molecular beam from a vaporizing solid. The system at NASA Glenn uses the restricted collimation method of Chatillon and colleagues, which consists of two apertures between the effusion cell and the ionizer. The diameter of the first aperture is smaller than the diameter of the effusion cell orifice, so the ionizer effectively only sees inside the effusion cell. The code is able to calculate the transmission coefficient through the cell orifice, through the cell orifice and the first aperture, and through the cell orifice and first and second aperatures. Calculated transmission coefficients through the cell orifice are compared to tabulated values to validate the code. Then transmission coefficients are calculated through the cell orifice and both apertures to the ionizer. This allows the geometry (aperture spacing and diameters) of the sampling system the sampling system to be optimized. Calculated transmission factors are also compared to literature values calculated via an analytic method.

Radke, Michael J.↗

NASA NTRS2016

Reaction of Basaltic Materials under High-Fidelity Venus Surface Conditions using the Glenn Extreme Environment Rig: First Results

Both historical and current investigations of Venus suggest that atmosphererock interactions play a critical role in the evolution of its atmosphere and crust. We have begun a series of systematic experiments designed to further our understanding of atmosphere-driven weathering and secondary mineralization of basaltic materials that may be occurring on Venus today. Our experiments expose representative igneous phases (mineral, glasses and rocks) to a high-fidelity simulation of Venus surface conditions using the NASA Glenn Extreme Environment Rig (GEER) located at the NASA Glenn Research Center in Cleveland, Ohio. GEER is a very large (800L) vessel capable of producing a long-term, high fidelity simulation of both the physical conditions (750 K and 92 bar) and atmospheric chemistry (down to the ppb-level) asso-ciated with the Venusian surface. As of this writing we have just finished the first of several planned experiments: a 42-day exposure of selected mineral, rocks and volcanic glasses. Our goal is to identify and prioritize the reactions taking place and better our understanding of their importance in Venus' climate history.

Venus surface↗

NASA NTRS2015

Thermodynamics and Kinetics of Silicate Vaporization

Silicates are a common class of materials that are often exposed to high temperatures. The behavior of these materials needs to be understood for applications as high temperature coatings in material science as well as the constituents of lava for geological considerations. The vaporization behavior of these materials is an important aspect of their high temperature behavior and it also provides fundamental thermodynamic data. The application of Knudsen effusion mass spectrometry (KEMS) to silicates is discussed. There are several special considerations for silicates. The first is selection of an appropriate cell material, which is either nearly inert or has well-understood interactions with the silicate. The second consideration is proper measurement of the low vapor pressures. This can be circumvented by using a reducing agent to boost the vapor pressure without changing the solid composition or by working at very high temperatures. The third consideration deals with kinetic barriers to vaporization. The measurement of these barriers, as encompassed in a vaporization coefficient, is discussed. Current measured data of rare earth silicates for high temperature coating applications are discussed. In addition, data on magnesium-iron-silicates (olivine) are presented and discussed.

thermodynamics↗

NASA NTRS2015

Ultra High Temperature (UHT) SiC Fiber (Phase 2)

Silicon-carbide fiber-reinforced silicon-carbide ceramic matrix composites (SiCSiC CMC) are emerginglightweight re-usable structural materials not only for hot section components in gas turbine engines, but also for controlsurfaces and leading edges of reusable hypersonic vehicles as well as for nuclear propulsion and reactor components. Ithas been shown that when these CMC are employed in engine hot-section components, the higher the upper usetemperature (UUT) of the SiC fiber, the more performance benefits are accrued, such as higher operating temperatures,reduced component cooling air, reduced fuel consumption, and reduced emissions. The first generation of SiCSiC CMC with a temperature capability of 2200-2400F are on the verge of being introduced into the hot-section components ofcommercial and military gas turbine engines.Today the SiC fiber type currently recognized as the worlds best in terms ofthermo-mechanical performance is the Sylramic-iBN fiber. This fiber was previously developed by the PI at NASA GRC using patented processes to improve the high-cost commercial Sylramic fiber, which in turn was derived from anotherlow-cost low-performance commercial fiber. Although the Sylramic-iBN fiber shows state-of-the art creep and rupture resistance for use temperatures above 2550oF, NASA has shown by fundamental creep studies and model developmentthat its microstructure and creep resistance could theoretically be significantly improved to produce an Ultra HighTemperature (UHT) SiC fiber.This Phase II Seedling Fund effort has been focused on the key objective of effectively repeating the similar processes used for producing the Sylramic-iBN fiber using a design of experiments approach to first understand the cause of the less than optimum Sylramic-iBN microstructure and then attempting to develop processconditions that eliminate or minimize these key microstructural issues. In so doing, it is predicted that that theseadvanced process could result in an UHT SiC fiber with 20 times more creep resistance than the Sylramic-iBN fiber,which in turn would allow SiCSiC CMC to operate up to 2700oF and above, thereby further enhancing the performancebenefits of SiCSiC components in aero-propulsion engines. It was also envisioned that the fiber processes developedduring Phase II efforts would not only reduce production costs for the UHT fiber by using low-cost precursor fibers andcombined processes, but also allow the UHT fibers to be directly produced in preforms of the precursor fibers, possibly atthe facilities of the CMC fabricator.

SiC Ceramic Fiber↗

NASA NTRS2015

Experimental and Theoretical Studies of Volatile Metal Hydroxides

Modern superalloys used in the construction of turbomachinery contain a wide range of metals in trace quantities. In addition, metal oxides and silicon dioxide are used to form Thermal Barrier Coatings (TBC) to protect the underlying metal in turbine blades. Formation of volatile hydroxides at elevated temperatures is an important mechanism for corrosion of metal alloys or oxides in combustion environments (N. Jacobson, D. Myers, E. Opila, and E. Copland, J. Phys. Chem. Solids 66, 471-478, 2005). Thermodynamic data is essential to proper design of components of modern gas turbines. It is necessary to first establish the identity of volatile hydroxides formed from the reaction of a given system with high temperature water vapor, and then to determine the equilibrium pressures of the species under operating conditions. Theoretical calculations of reaction energies are an important check of experimental results. This presentation reports results for several important systems: Si-O-H, Cr-O-H, Al-O-H, Ti-O-H, and ongoing studies of Ta-O-H.

Thermal Barrier Coatings↗

NASA NTRS2014

High Temperature Chemistry at NASA: Hot Topics

High Temperature issues in aircraft engines Hot section: Ni and Co based Superalloys Oxidation and Corrosion (Durability) at high temperatures. Thermal protection system (TPS) and RCC (Reinforced Carbon-Carbon) on the Space Shuttle Orbiter. High temperatures in other worlds: Planets close to their stars.

re-entry heat shields↗

NASA NTRS2014

Experimental and Theoretical Study of Thermodynamics of the Reaction of Titania and Water at High Temperatures

The transpiration method was used to determine the volatility of titanium dioxide (TiO2) in water vapor-containing environments at temperatures between 1473 and 1673 K. Water contents ranged from 0 to 76 mole % in oxygen or argon carrier gases for 20 to 250 hr exposure times. Results indicate that oxygen is not a key contributor to volatilization and the primary reaction for volatilization in this temperature range is: TiO2(s) + H2O(g) = TiO(OH)2(g). Data were analyzed with both the second and third law methods to extract an enthalpy and entropy of formation. The geometry and vibrational frequencies of TiO(OH)2(g) were computed using B3LYP density functional theory, and the enthalpy of formation was computed using the coupled-cluster singles and doubles method with a perturbative correction for connected triple substitutions [CCSD(T)]. Thermal functions are calculated using both a structure with bent and linear hydroxyl groups. Calculated second and third heats show closer agreement with the linear hydroxyl group, suggesting more experimental and computational spectroscopic and structural work is needed on this system.

equilibrium↗

NASA NTRS2013

Oxygen Permeability and Grain-Boundary Diffusion Applied to Alumina Scales

High-temperature oxygen permeability measurements had determined grain-boundary diffusivities (deltaD(sub gb)) in bulk polycrystalline alumina (Wada, Matsudaira, and Kitaoka). They predict that oxygen deltaD(sub gb,O) varies with oxygen pressure as P(O2)(sup -1/6) at low pressure whereas aluminum deltaD(sub gb),Al varies with P(O2)(sup +3/16) at high pressure. These relations were used to evaluate alumina scale growth in terms of diffusivity and grain size. A modified Wagner treatment for dominant inward oxygen growth produces the concise solution: П(sub i) = k(sub p,i)×G(sub i) = 12 deltaD(sub gb,O,int), where П(sub i) is a constant and k(sub p,i) and G(sub i) refer to instantaneous values of the scale parabolic growth constant and grain size, respectively. A commercial FeCrAl(Zr) alloy was oxidized at 1100 to 1400 degC to determine k(sub p,i), interfacial grain size, П, and thus deltaD(sub gb,O,int). The deltaD(sub gb,O,int) values predicted from oxidation at (375 kJ/mole) were about 20 times less than those obtained above (at 298 kJ/mole), but closer than extrapolations from high-temperature bulk measurements. The experimental oxidation results agree with similar FeCrAl(X) studies, especially where both k(sub p,i) and G(sub i) were characterized. This complete approach accounts for temperature-sensitive oxidation effects of grain enlargement, equilibrium interface pressure variation, and grain-boundary diffusivity.

Smialek, James L.↗

NASA NTRS2012

Mass Spectrometric Studies of Oxides

Current studies at NASA Glenn on oxide thermodynamics are discussed. Previous studies on the vaporization of B2O3 in reducing atmospheres led to inconsistent studies when B was used as a reductant. It is shown that liquid B2O3 does not wet B and a clear phase separation was noted in the Knudsen cell. This problem was solved by using FeB and Fe2B to supply a different and constant activity of B. The thermodynamic data thus derived are compared to quantum chemical composite calculations. A major problem in high temperature mass spectrometry is the determination of accurate ionization cross sections, particularly for molecules. The method of Deutsch and Mark shows promise and some sample calculations are discussed. Finally current studies on the thermodynamics of rare earth silicates are discussed. Here the problems are obtaining a measurable signal from SiO2 vaporization and non-equilibrium vaporization. The use of a Ta reducing agent provides a stronger signal, which is related to silica activity. The Whitman-Motzfeld relation adapted to KEMS measurements is applied to obtain equilibrium pressures.

Jacobson, Nathan S.↗

NASA NTRS2011

Hysteresis in the Active Oxidation of SiC

Si and SiC show both passive oxidation behavior where a protective film of SiO2 forms and active oxidation behavior where a volatile suboxide SiO(g) forms. The active-to-passive and passive-to-active oxidation transitions are explored for both Si and SiC. Si shows a dramatic difference between the P(O2) for the two transitions of ~10-4 bar. The active-to-passive transition is controlled by the condition for SiO2/Si equilibrium and the passive-to-active transition is controlled by the decomposition of SiO2. In the case of SiC, the P(O2) for these transitions are much closer. The active-to-passive transition appears to be controlled by the condition for SiO2/SiC equilibrium. The passive-to-active transition appears to be controlled by the interfacial reaction of SiC and SiO2 and subsequent generation of gases at the interface which leads to scale breakdown.

Jacobson, Nathan S.↗

NASA NTRS2011

The Vaporization of B2O3(l) to B2O3(g) and B2O2(g)

The vaporization of B2O3 in a reducing environment leads to formation of both B2O3(g) and B2O2(g). While formation of B2O3(g) is well understood, many questions about the formation of B2O2(g) remain. Previous studies using B(s) + B2O3(l) have led to inconsistent thermodynamic data. In this study, it was found that after heating, B(s) and B2O3(l) appear to separate and variations in contact area likely led to the inconsistent vapor pressures of B2O2(g). To circumvent this problem, an activity of boron is fixed with a two-phase mixture of FeB and Fe2B. Both second and third law enthalpies of formation were measured for B2O2(g) and B2O3(g). From these the enthalpies of formation at 298.15 K are calculated to be -479.9 +/- 41.5 kJ/mol for B2O2(g) and -833.4 +/- 13.1 kJ/mol for B2O3(g). Ab initio calculations to determine the enthalpies of formation of B2O2(g) and B2O3(g) were conducted using the W1BD composite method and show good agreement with the experimental values.

Jacobson, Nathan S.↗

NASA NTRS2011

Active Oxidation of SiC

The high temperature oxidation of silicon carbide occurs in either a passive or active mode, depending on temperature and oxygen potential. Passive oxidation forms a protective oxide film which limits attack of the SiC:SiC(s) + 3/2 O2(g) = SiO2(s) + CO(g.) Active oxidation forms a volatile oxide and leads to extensive attack of the SiC: SiC(s) + O2(g) = SiO(g) + CO(g). The transition points and rates of active oxidation are a major issue. Previous studies are reviewed and the leading theories of passive/active transitions summarized. Comparisons are made to the active/passive transitions in pure Si, which are relatively well-understood. Critical questions remain about the difference between the active-to-passive transition and passive-to-active transition. For Si, Wagner [2] points out that the active-to-passive transition is governed by the criterion for a stable Si/SiO2 equilibria and the passive-to-active transition is governed by the decomposition of the SiO2 film. This suggests a significant oxygen potential difference between these two transitions and our experiments confirm this. For Si, the initial stages of active oxidation are characterized by the formation of SiO(g) and further oxidation to SiO2(s) as micron-sized rods, with a distinctive morphology. SiC shows significant differences. The active-to-passive and the passive-to-active transitions are close. The SiO2 rods only appear as the passive film breaks down. These differences are explained in terms of the reactions at the SiC/SiO2 interface. In order to understand the breakdown of the passive film, pre-oxidation experiments are conducted. These involve forming dense protective scales of 0.5, 1, and 2 microns and then subjecting the samples with these scales to a known active oxidation environment. Microstructural studies show that SiC/SiO2 interfacial reactions lead to a breakdown of the scale with a distinct morphology.

Jacobson, Nathan S.↗

NASA NTRS2010

Measuring Thermodynamic Properties of Metals and Alloys With Knudsen Effusion Mass Spectrometry

This report reviews Knudsen effusion mass spectrometry (KEMS) as it relates to thermodynamic measurements of metals and alloys. First, general aspects are reviewed, with emphasis on the Knudsen-cell vapor source and molecular beam formation, and mass spectrometry issues germane to this type of instrument are discussed briefly. The relationship between the vapor pressure inside the effusion cell and the measured ion intensity is the key to KEMS and is derived in detail. Then common methods used to determine thermodynamic quantities with KEMS are discussed. Enthalpies of vaporization, the fundamental measurement, are determined from the variation of relative partial pressure with temperature using the second-law method or by calculating a free energy of formation and subtracting the entropy contribution using the third-law method. For single-cell KEMS instruments, measurements can be used to determine the partial Gibbs free energy if the sensitivity factor remains constant over multiple experiments. The ion-current ratio method and dimer-monomer method are also viable in some systems. For a multiple-cell KEMS instrument, activities are obtained by direct comparison with a suitable component reference state or a secondary standard. Internal checks for correct instrument operation and general procedural guidelines also are discussed. Finally, general comments are made about future directions in measuring alloy thermodynamics with KEMS.

Copland, Evan H.↗