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Jacobson, Nathan S.

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

At least 55 records · Page 3

Thermodynamic Modeling of the YO(l.5)-ZrO2 System

The YO1.5-ZrO2 system consists of five solid solutions, one liquid solution, and one intermediate compound. A thermodynamic description of this system is developed, which allows calculation of the phase diagram and thermodynamic properties. Two different solution models are used-a neutral species model with YO1.5 and ZrO2 as the components and a charged species model with Y(+3), Zr(+4), O(-2), and vacancies as components. For each model, regular and sub-regular solution parameters are derived fiom selected equilibrium phase and thermodynamic data.

Jacobson, Nathan S.↗

Knudsen Cell Studies of Ti-Al Thermodynamics

In this paper we describe the Knudsen cell technique for measurement of thermodynamic activities in alloys. Numerous experimental details must be adhered to in order to obtain useful experimental data. These include introduction of an in-situ standard, precise temperature measurement, elimination of thermal gradients, and precise cell positioning. Our first design is discussed and some sample data on Ti-Al alloys is presented. The second modification and associated improvements are also discussed.

Jacobson, Nathan S.↗

Thermodynamic Assessment of the Y2o3-yb2o3-zro2 System

Yttria-zirconia (Y2O3-ZrO2) is the most widely used of the rare earth oxide-zirconia systems. There are numerous experimental studies of the phase boundaries in this system. In this paper, we assess these data and derive parameters for the solution models in this system. There is current interest in other rare earth oxide-zirconia systems as well as systems with several rare earth oxides and zirconia, which may offer improved properties over the Y2O3-ZrO2 system. For this reason, we also assess the ytterbia-zirconia (Yb2O3-ZrO2) and Y2O3-Yb2O3-ZrO2 system.

Jacobson, Nathan S.↗

Computational Thermodynamic Study to Predict Complex Phase Equilibria in the Nickel-Base Superalloy Rene N6

A previous study by Ritzert et al. on the formation and prediction of topologically closed packed (TCP) phases in the nickel-base superalloy Rene' N6 is re-examined with computational thermodynamics. The experimental data on phase distribution in forty-four alloys with a composition within the patent limits of the nickel-base superalloy Rene' N6 provide a good basis for comparison to and validation of a commercial nickel superalloy database used with ThermoCalc. Volume fraction of the phases and partitioning of the elements are determined for the forty-four alloys in this dataset. The baseline heat treatment of 400 h at 1366 K was used. This composition set is particularly interesting since small composition differences lead to dramatic changes in phase composition. In general the calculated values follow the experimental trends. However, the calculations indicated no TCP phase formation when the experimental measurements gave a volume percent of TCP phase less than 2 percent. When TCP phases were predicted, the calculations under-predict the volume percent of TCP phases by a factor of 2 to 8. The calculated compositions of the gamma and gamma' phases show fair agreement with the measurements. However, the calculated compositions of the P Phase do not agree with those measured. This may be due to inaccuracies in the model parameters for P phase and/or issues with the microprobe analyses of these phases. In addition, phase fraction diagrams and sigma and P phase solvus temperatures are calculated for each of the alloys. These calculations indicate that P phase is the primary TCP phase formed for the alloys considered here at 1366 K. Finally, a series of isopleths are calculated for each of the seven alloying elements. These show the effect of each alloying element on creating TCP phases.

Copland, Evan H.↗

Thermodynamic Database for the NdO(1.5)-YO(1.5)-YbO(1.5)-ScO(1.5)-ZrO2 System

A database for YO(1.5)-NdO(1.5)-YbO(1.5)-ScO(1.5)-ZrO2 for ThermoCalc (ThermoCalc AB, Stockholm, Sweden) has been developed. The basis of this work is the YO(1.5)-ZrO2 assessment by Y. Du, Z. Jin, and P. Huang, 'Thermodynamic Assessment of the ZrO2-YO(1.5) System'. Experimentally only the YO(1.5)-ZrO2 system has been well-studied. All other systems are only approximately known. The major simplification in this work is the treatment of each single cation unit as a component. The pure liquid oxides are taken as reference states and two term lattice stability descriptions are used for each of the components. The limited experimental phase diagrams are reproduced.

Jacobson, Nathan S.↗

Thermodynamics of Titanium-Aluminum-Oxygen Alloys Studied

Titanium-aluminum alloys are promising intermediate-temperature alloys for possible compressor applications in gas-turbine engines. These materials are based on the a2-Ti3Al + g-TiAl phases. The major issue with these materials is high oxygen solubility in a2-Ti3Al, and oxidation of unsaturated alloys generally leads to mixed non-protective TiO2+Al2O3 scales. From phase diagram studies, oxygen saturated a2-Ti3Al(O) is in equilibrium with Al2O3; however, oxygen dissolution has a detrimental effect on mechanical properties and cannot be accepted. To better understand the effect of oxygen dissolution, we examined the thermodynamics of titanium-aluminum-oxygen alloys.

Copland, Evan H.↗

Thermodynamics of Volatile Silicon Hydroxides Studied

Silicon-based ceramics are promising candidate structural materials for heat engines. The long-term stability of these materials to environmental degradation is dependent on the formation and retention of a protective SiO2 layer. It is well known that SiO2 forms stable volatile hydroxides in the presence of water vapor at elevated temperatures. Combustion conditions, which characteristically are at high velocities, contain significant water vapor pressures, and high temperatures tend to promote continuous formation of these hydroxides with resulting material degradation. For the degradation of silicon-based ceramics to be predicted, accurate thermodynamic data on the formation of silicon hydroxides are needed.

Copland, Evan H.↗

Calculation of Phase Equilibria in the Y2O3-Yb2O3-ZrO2 System

Rare earth oxide stabilized zirconias find a wide range of applications. An understanding of phase equilibria is essential to all applications. In this study, the available phase boundary data and thermodynamic data is collected and assessed. Calphad-type databases are developed to completely describe the Y2O3-ZrO2, Yb2O3-ZrO2, and Y2O3-Yb2O3 systems. The oxide units are treated as components and regular and subregular solution models are used. The resultant calculated phase diagrams show good agreement with the experimental data. Then the binaries are combined to form the database for the Y2O3-Yb2O3-ZrO2 psuedo-ternary.

Jacobson, Nathan S.↗

Thermodynamics of Silicon-Hydroxide Formation in H2O Containing Atmospheres

The formation of volatile silicon-hydroxide species from SiO2 in water containing atmospheres has been identified as a potentially important mode of degradation of Si-based ceramics. Availability of thermodynamic data for these species is a major problem. This study is part of an ongoing effort to obtain reliable, experimentally determined thermodynamic data for these species. The transpiration method was used to measure the pressure of Si-containing vapor in equilibrium with SiO2 (cristobalite) and Ar + H2O(g) with various mole fractions of water vapor, X(sub H2O), at temperatures ranging from 1000 to 1780 K. Enthalpies and entropies for the reaction, SiO2(s) + 2H2O(g) = Si(OH)4(g), were obtained, at X(sub H2O) = 0.15 and 0.37, from the variation of lnK with 1/T according to the 'second law method'. The following data were obtained: delta(H)deg = 52.9 +/- 3.7 kJ/mole and delta(S)deg = -68.6 +/- 2.5 J/mole K at an average temperature of 1550 K, and delta(H)deg = 52.5+/-2.0 kJ/mole and delta(S)deg= -69.7 +/- 1.5 J/moleK at an average temperature of 1384 K, for X(sub H2O)= 0.15 and 0.37, respectively. These data agree with results from the literature obtained at an average temperature of 1600 K, and strongly suggest Si(OH)4(g) is the dominant vapor species. Contradictory results were obtained with the determination of the dependence of Si-containing vapor pressure on the partial pressure of water vapor at 1187 and 1722 K. These results suggested the Si-containing vapor could be a mixture of Si(OH)4 + SiO(OH)2. Further pressure dependent studies are in progress to resolve these issues.

Copland, Evan↗

Thermodynamic Activity Measurements with Knudsen Cell Mass Spectrometry

Coupling the Knudsen effusion method with mass spectrometry has proven to be one of the most useful experimental techniques for studying the equilibrium between condensed phases and complex vapors. The Knudsen effusion method involves placing a condensed sample in a Knudsen cell, a small "enclosure", that is uniformly heated and held until equilibrium is attained between the condensed and vapor phases. The vapor is continuously sampled by effusion through a small orifice in the cell. A molecular beam is formed from the effusing vapor and directed into a mass spectrometer for identification and pressure measurement of the species in the vapor phase. Knudsen cell mass spectrometry (KCMS) has been used for nearly fifty years now and continues to be a leading technique for obtaining thermodynamic data. Indeed, much of the well-established vapor specie data in the JANAF tables has been obtained from this technique. This is due to the extreme versatility of the technique. All classes of materials can be studied and all constituents of the vapor phase can be measured over a wide range of pressures (approximately 10(exp -4) to 10(exp -11) bar) and temperatures (500-2800 K). The ability to selectively measure different vapor species makes KCMS a very powerful tool for the measurement of component activities in metallic and ceramic solutions. Today several groups are applying KCMS to measure thermodynamic functions in multicomponent metallic and ceramic systems. Thermodynamic functions, especially component activities, are extremely important in the development of CALPHAD (Calculation of Phase Diagrams) type thermodynamic descriptions. These descriptions, in turn, are useful for modeling materials processing and predicting reactions such as oxide formation and fiber/matrix interactions. The leading experimental methods for measuring activities are the Galvanic cell or electro-motive force (EMF) technique and the KCMS technique. Each has specific advantages, depending on material and conditions. The EMF technique is suitable for lower temperature measurements, provided a suitable cell can be constructed. KCMS is useful for higher temperature measurements in a system with volatile components. In this paper, we briefly review the KCMS technique and identify the major experimental issues that must be addressed for precise measurements. These issues include temperature measurements, cell material and cell design and absolute pressure calibration. The resolution of these issues are discussed together with some recent examples of measured thermodynamic data.

Copland, Evan H.↗

Formation of Leading-Edge Pinholes in the Space Shuttle Wings Investigated

The space shuttle wing leading edge and nose cap are composed of a carbon/carbon composite that is protected by silicon carbide. The coefficient of thermal expansion mismatch leads to cracks in the silicon carbide. The outer coating of the silicon carbide is a sodium-silicate-based glass that becomes fluid at the shuttles high reentry temperatures and fills these cracks. Small pinholes roughly 0.1 mm in diameter have been observed on these materials after 12 or more flights. These pinholes have been investigated by researchers at the NASA Johnson Space Center, Rockwell International, the Boeing Company, Lockheed Martin Corporation, and the NASA Glenn Research Center at Lewis Field to determine the possible sources and the extent of damage. A typical pinhole is illustrated in the photomicrographs. These pinholes are found primarily on the wing leading edges and not on the nose cap, which is covered when the orbiter is on the launch pad. The pinholes are generally associated with a bead of zincrich glass. Examination of the orbiter and launch structure indicates that weathering paint on the launch structure leads to deposits of zinc-containing paint flakes on the wing leading edge. These may become embedded in the crevices of the wing leading edge and form the observed zinc-rich glass. Laboratory experiments indicate that zinc oxide reacts vigorously with the glass coating on the silicon carbide. Thus, it is likely that this is the reaction that leads to pinhole formation (Christensen, S.V.: Reinforced Carbon/Carbon Pin Hole Formation Through Zinc Oxide Attack. Rockwell International Internal Letter, RDW 96 057, May 1996). Cross-sectional examination of pinholes suggests that they are enlarged thermal expansion mismatch cracks. This is illustrated in the photomicrographs. A careful microstructural analysis indicates that the pinhole walls consist of layers of zinc-containing glass. Thus, pinholes are likely formed by zinc oxide particles lodging in crevices and forming a corrosive zinc-rich glass that enlarges existing cracks. Having established the likely source of the pinholes, we next needed to model the damage. Our concern was that if a pinhole went through the silicon carbide to the carbon/carbon substrate, oxygen would have a clear path to oxidize the carbon at high temperatures. This possibility was examined with studies in a laboratory furnace. An ultrasonic drill was used to make artificial pinholes in a sample of protected carbon/carbon. After exposure, the specimens were weighed and cross-sectioned to quantify the extent of oxidation below the pinhole. The results at higher temperatures showed good agreement with a simple diffusion-control model. This model is based on the two-step oxidation of carbon to carbon monoxide and carbon dioxide. The fluxes are illustrated in the final figure. The model indicates a strong dependence on pinhole diameter. For smaller diameters and short times, the oxidation of carbon is very limited.

Jacobson, Nathan S.↗

Rhenium-Oxygen Interactions at High Temperatures

The reaction of pure rhenium metal with dilute oxygen/argon mixtures was studied from 600 to 1400 C. Temperature, oxygen pressure, and flow rates were systematically varied to determine the rate-controlling steps. At lower temperatures the oxygen/rhenium chemical reaction is rate limiting; at higher temperatures gas-phase diffusion of oxygen through the static boundary layer is rate limiting. At all temperatures post-reaction microstructures indicate preferential attack along certain crystallographic planes and defects.

Jacobson, Nathan S.↗