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On the low-lying states of TiC

The ground and low-lying excited states of TiC are investigated using a CASSCF-externally contracted CI approach. The calculations yield a 3Sigma(+) ground state, but the 1Sigma(+) state is only 780/cm higher and cannot be ruled out. The low-lying states have some triple bond character. The nature of the bonding and origin of the states are discussed.

Bauschlicher, C. W., Jr.↗

Characteristics of fluid flow in the combustion synthesis of TiC from the elements

The results of a numerical investigation of finite reservoir effects on capillary spreading at small reservoir dimensions are presently related to wave propagation phenomena in the combustion synthesis of TiC from its two elemental constituents. It is noted that gravitational forces can affect bubble coalescence by nonbuoyant means under the suitable conditions, although these conditions are expected to be rare in combustion synthesis. Finite-curved reservoirs can drive capillary flow due to surface tension and wall contact forces; these cause the wall and the metal to be completely reconfigured during combustion synthesis.

Valone, S. M.↗

TiC growth in C fiber/Ti alloy composites during liquid infiltration

A cylindrical model is developed for predicting the reaction zone thickness of carbon fiber-reinforced Ti-matrix composites, and good agreement is obtained between its predicted values and experimental results. The reaction-rate constant for TiC formation is estimated to be 1.5 x 10 exp -9 sq cm/sec. The model is extended to evaluate the relationship between C-coating thicknesses on SiC fibers and processing times.

Warrier, S. G.↗

TIC 172900988: A Transiting Circumbinary Planet Detected in One Sector of TESS Data

We report the first discovery of a transiting circumbinary planet detected from a single sector of Transiting Exoplanet Survey Satellite (TESS) data. During Sector 21, the planet TIC 172900988b transited the primary star and then five days later it transited the secondary star. The binary is itself eclipsing, with a period P ≈ 19.7 days and an eccentricity e ≈ 0.45. Archival data from ASAS-SN, Evryscope, KELT, and SuperWASP reveal a prominent apsidal motion of the binary orbit, caused by the dynamical interactions between the binary and the planet. A comprehensive photodynamical analysis of the TESS, archival and follow-up data yields stellar masses and radii of M(1) = 1.2384 ± 0.0007 Mꙩ and R(1) = 1.3827 ± 0.0016 Rꙩ for the primary and M(2) = 1.2019 ± 0.0007 Mꙩ and R(2) = 1.3124 ± 0.0012 Rꙩ for the secondary. The radius of the planet is R(3) = 11.25 ± 0.44 Rꚛ (1.004 ± 0.039R(Jup)). The planet’s mass and orbital properties are not uniquely determined—there are six solutions with nearly equal likelihood. Specifically, we find that the planet’s mass is in the range of 824 ≲ M3 ≲ 981 Mꚛ (2.65 ≲ M3 ≲ 3.09M(Jup)), its orbital period could be 188.8, 190.4, 194.0, 199.0, 200.4, or 204.1 days, and the eccentricity is between 0.02 and 0.09. At V = 10.141 mag, the system is accessible for high-resolution spectroscopic observations, e.g., the Rossiter–McLaughlin effect and transit spectroscopy.

Veselin B. Kostov↗

Stacking faults in TiC.

Stacking faults in titanium carbide shown by electron microscopy bounded by partial dislocations

TITANIUM CARBIDE↗

Carbide coated fibers in graphites-aluminum composites

Research activities are described for a NASA-supported program at the Los Alamos Scientific Laboratory to develop graphite fiber-aluminum matrix composites. A chemical vapor deposition apparatus was constructed for continuously coating graphite fibers with TiC. As much as 150 meters of continuously coated fibers were produced. Deposition temperatures were varied from 1365 K to about 1750 K, and deposition time from 6 to 150 seconds. The 6 sec deposition time corresponded to a fiber feed rate of 2.54 m/min through the coater. Thin, uniform, adherent TiC coats, with thicknesses up to approximately 0.1 micrometer were produced on the individual fibers of Thornel 50 graphite yarns without affecting fiber strength. Although coat properties were fairly uniform throughout a given batch, more work is needed to improve the batch-to-batch reproducibility. Samples of TiC-coated Thornel 50 fibers were infiltrated with an aluminum alloy and hot-pressed in vacuum to produce small composite bars for flexure testing. Strengths as high as 90% of the rule-of-mixtures strength were achieved. Results of the examination of the fracture surfaces indicate that the bonding between the aluminum and the TiC-coated fibers is better than that achieved in a similar, commercially infiltrated material made with fibers having no observable surface coats. Several samples of Al-infiltrated, TiC-coated Thornel 50 graphite yarns, together with samples of the commercially infiltrated, uncoated fibers, were heated for 100 hours at temperatures near the alloy solidus. The TiC-coated samples appear to undergo less reaction than do the uncoated samples. Photomicrographs are shown.

Imprescia, R. J.↗

Stability of Titanium Nitride and Titanium Carbide When Exposed to Hydrogen Atoms from 298 to 1950 K

Titanium nitride and titanium carbide deposited on tungsten wires were exposed to hydrogen atoms (10(exp -4) atm pressure) produced by the action of microwave radiation on molecular hydrogen. The results of these experiments in the temperature range 298 to 1950 K indicate that no appreciable reaction takes place between atomic hydrogen and TiN or TiC. The formation of reaction products (NH3, CH4, C2H2) should be favored at lower temperatures. However, because of the high catalytic activity of Ti for H atom recombination, the rate of such reactions with H atoms is controlled by the rate of evaporation of Ti from the surface, this rate being low at temperatures below 1200 K. In order to interpret the stability of TiN and TiC in H atoms more fully, the stability of TiN and TiC in vacuum and H2 gas was also studied. The thermodynamic computations conform in order of magnitude to the experimentally found rates of decomposition of TiN and TiC in vacuum and are also consistent with the fact that no appreciable reaction is found with these compounds in molecular H2 at a pressure of 10(exp -3) atmosphere in the temperature range 2980 to 2060 K. When TiN or TiC was heated in atomic H or molecular H2, no reaction products other than those obtained from the simple decomposition of the nitride and carbide were observed. The gaseous products were analyzed in a mass spectrometer.

Philipp, Warren H.↗

Comparison of Two Methods for Noninvasive Determination of Stroke Volume During Orthostatic Challenge

Background: The real time, beat-by-beat, non-invasive determination of stroke volume (SV) is an important parameter in many aerospace related physiologic protocols. In this study, we compared simultaneous estimates of SV calculated from peripheral pulse waveforms with a more conventional non-invasive technique. Methods: Using a prospective, randomized blinded protocol, ten males and nine females completed 12-mm tilt table protocols. The relative change (%(Delta)) in beat-to-beat SV was estimated non-invasively from changes in pulse waveforms measured by application of infrared finger photoplethysmography (IFP) with a Portapres(Registered TradeMark) blood pressure monitoring device and by thoracic impedance cardiography (TIC). The %(Delta) SV values were calculated from continuous SV measurements in the supine posture and over the first 10 s (T1), second 10 s (T2), and 3.5 minutes (T3) of 80deg head-up tilt (HUT). Results: The average %(Delta) SV measured by IFP at T1 (-11.7 +/- 3.7 %) was statistically less (P <0.02) than the average %(Delta) SV measured by TIC at T1 (-21.7 +/- 3.1 %), while the average %(Delta) SV measured by 1FF at T2 (-16.2 +/- 3.9 %) and T3 (-19.1 +/- 3.8 %) were not statistically distinguishable (P > or = 0.322) than the average %(Delta) SV measured by TIC at T2 (-21.8 +/- 2.5 %), and T3 (-22.6 +/- 2.9 %). Correlation coefficients (r(sup 2)) between IFP and TIC were 0.117 (T1), 0.387 (T2), and 0.7 18 (T3). Conclusion: IFP provides beat-to-beat (real time) assessment of %(Delta) SV after 20 sec of transition to an orthostatic challenge that is comparable to the commonly accepted TIC. Our data support the notion that IFP technology which has flown during space missions can be used to accurately assess physiological status and countermeasure effectiveness for orth static problems that may arise in astronauts after space flight. While the peripherally measured IFP response is slightly delayed, the ease of implementing this monitor in the field is advantageous.

Doerr, Donald F.↗

Melting and solidification dynamics during laser melting of reaction-based metal matrix composites uncovered by in-situ synchrotron X-ray diffraction

Laser additive manufacturing (AM) of reaction-based metal matrix composites (MMCs) involves highly complex and non-equilibrium material transformation behavior, including melting, dissolution, precipitation, and solidification. Yet, the dynamics and interplay of these phase transformation processes remain poorly understood, posing substantial challenges in identifying the microstructure formation mechanism, and predicting and controlling the microstructure in the printed parts. Here, in this study, we performed the in-situ X-ray diffraction experiment to characterize the phase evolution dynamics of the 316L + 10 vol.%TiC system during laser melting, which provides direct and quantitative insights of the complex phase reaction and evolution dynamics under rapid heating and cooling conditions relevant to additive manufacturing of reaction-based MMCs. Further in-depth thermodynamic and kinetic calculations revealed that most of the phase evolution behavior observed in the in-situ X-ray diffraction experiment cannot be solely explained by widely used equilibrium thermodynamic models, and diffusion-controlled nonequilibrium dissolution and precipitation kinetics must be considered to elucidate the complex phase evolution behavior, including incomplete TiC dissolution, and three-step TiC precipitation. The three distinct types of precipitates generate unique hierarchical TiC micro- and nanostructures, which enhances the yield strength from 513 MPa to 877 MPa by 71 %, tensile strength from 628 MPa to 1054 MPa by 68 %, and Young's modulus from 193 GPa to 221 GPa by 14 %. The findings of our research provide the knowledge foundation for the design of unique microstructures and advanced MMC materials through laser AM.

36 MATERIALS SCIENCE↗

Investigation of Electrocatalytic CO 2 Reduction on MXene Materials via First-Principles Simulations

Computational studies of CO 2 reduction to yield various products were carried out on the basal plane and edges of different MXene materials. The impact of vacancies upon Mo 2 TiC 2 T x , W 2 TiC 2 T x , and Ti 3 C 2 T x (T x = O and OH) was also examined for both edge and basal sites. Initial calibrations were carried out to generate surfaces with optimal oxide/hydroxide ratios and proper termination sites upon which various vacancy sites were explored to ensure an accurate model of the surfaces’ resting states. From this work, Mo 2 TiC 2 O was determined to exhibit the lowest theoretical overpotential for methane as determined by volcano plot analyses. At a large enough vacancy concentration, the CO 2 reduction reaction (CO 2 RR) is predicted to outcompete the hydrogen evolution reaction (HER) as the predominant reaction on the surface. In conclusion, when examining the edge of Mo 2 TiC 2 O, stronger CO 2 binding was exhibited to such an extent that the reaction was predicted to terminate after the generation of formate on the edge.

Lund, Colton [Argonne National Laboratory (ANL), A↗

Carbon-carbon interactions in warm dense titanium carbide

Encouraged by experimental reports of diamond precipitation in carbon-containing materials under warm dense matter conditions and in shock compression experiments, we examine the behavior of carbon in TiC using density functional theory-molecular dynamics simulations. Two polymorphs of TiC are considered, the ambient-pressure B1 ($Fm$$\overline{3}$$m$) structure in which C-C interactions are prevented by geometric constraints, and a high-pressure Cmcm structure in which C atoms condense into zigzag chains. Chemistry-inspired bonding analyses confirm the covalently bound nature of these chains and further illuminate important interatomic interactions in both structures. Upon melting of B1 TiC, new short-range C-C interactions develop in the liquid, while the pre-existing C-C interactions in Cmcm TiC persist in the liquid. Here, the resulting carbon networks in the melt provide a promising environment for eventual diamond nucleation.

Ab initio molecular dynamics↗