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At least 19 records

Design and chemical synthesis of iodine-containing molecules for application to solar-pumped I* lasers

This work is directed toward the design and chemical synthesis of new media for solar-pumped I* lasers. In view of the desirability of preparing a perfluoroalkyl iodide absorbing strongly at 300 nm, the relationship betwen perfluoroalkyl iodide structure and the corresponding absorption wavelength was reexamined. Analysis of existing data suggests that, in this family of compounds, the absorption maximum shifts to longer wavelength, as desired, as the C-I bond in the lasant is progressively weakened. Weakening of the C-I bond correlates, in turn, with increasing stability of the perfluoroalkyl radical formed upon photodissociation of the iodide. The extremely promising absorption characteristics of perfluoro-tert-butyl iodide can be accounted for on this basis. A new technique of diode laser probing to obtain precise yields of I* atoms in photodissociation was also developed.

Shiner, C. S.↗

Propulsion Control and Health Management (PCHM) Technology for Flight Test on the C-17 T-1 Aircraft

The C-I 7 T-l Globemaster III is an Air Force flight research vehicle located at Edwards Air Force Base. NASA Dryden and the C-17 System Program Office have entered into a Memorandum of Agreement to permit NASA the use of the C-I 7 T-I to conduct flight research on a mutually coordinated schedule. The C-17 Propulsion Control and Health Management (PCHM) Working Group was formed in order to foster discussion and coordinate planning amongst the various government agencies conducting PCHM research with a potential need for flight testing, and to communicate to the PCHM community the capabilities of the C-17 T-l aircraft to support such flight testing. This paper documents the output of this Working Group, including a summary of the candidate PCHM technologies identified and their associated benefits relative to NASA goals and objectives.

Simon, Donald L.↗

Probing C–I bond fission in the UV photochemistry of 2-iodothiophene with core-to-valence transient absorption spectroscopy

The UV photochemistry of small heteroaromatic molecules serves as a testbed for understanding fundamental photo-induced chemical transformations in moderately complex compounds, including isomerization, ring-opening, and molecular dissociation. Here, a combined experimental-theoretical study of 268 nm UV light-induced dynamics in 2-iodothiophene (C 4 H 3 IS) is performed. The dynamics are experimentally monitored with a femtosecond extreme ultraviolet (XUV) probe that measures iodine N-edge 4d core-to-valence transitions. Experiments are complemented by density functional theory calculations of both the pump-pulse induced valence excitations and the XUV probe-induced core-to-valence transitions. Possible intramolecular relaxation dynamics are investigated by ab initio molecular dynamics simulations. Furthermore, gradual absorption changes up to ~0.5 to 1 ps after excitation are observed for both the parent molecular species and emerging iodine fragments, with the latter appearing with a characteristic rise time of 160 ± 30 fs. Comparison of spectral intensities and energies with the calculations identifies an iodine dissociation pathway initiated by a predominant π → π* excitation. In contrast, initial excitation to a nearby n ⟂ → σ* state appears unlikely based on a significantly smaller oscillator strength and the absence of any corresponding XUV absorption signatures. Excitation to the π → π* state is followed by contraction of the C–I bond, enabling a nonadiabatic transition to a dissociative π→σ C-I * state. For the subsequent fragmentation, a relatively narrow bond-length region along the C–I stretch coordinate between 230 and 280 pm is identified, where the transition between the parent molecule and the thienyl radical + iodine atom products becomes prominent in the XUV spectrum due to rapid localization of two singly occupied molecular orbitals on the two fragments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct momentum imaging of charge transfer following site-selective ionization

We study ultrafast charge rearrangement in dissociating 2-iodopropane (2-C 3 H 7 I) using site-selective core-ionization at the iodine atom. Clear signatures of electron transfer between the neutral propyl fragment and multiply charged iodine ions are observed in the recorded delay-dependent ion momentum distributions. The detected charge transfer pathway is only favorable within a small (few angstrom), charge-state-dependent spatial window located at C-I distances longer than that of the neutral ground-state molecule. Lastly, these results offer new insights into the physics underpinning charge transfer in isolated molecules and pave the way for a new class of time-resolved studies.

74 ATOMIC AND MOLECULAR PHYSICS↗

Investigation of the excited state iodine lifetime in the photodissociation of perfluoroalkyl iodides

An evaluation of prospective laser materials for a space-based solar pumped laser system over the past decade has resulted in the identification of the iodine photodissociation laser as that system best suited to solar-pumped high energy operation. The active medium for the solar-pumped iodine photodissociation laser is from the family of perfluoroalkyl iodides. These lasants have the general form C(n)F(2n + 1)I, often abbreviated as RI. These iodides are known to exhibit photodissociaiton of the C-I bond when irradiated by near UV photons. The focus was on the experimental determination of the lifetime of the excited iodine atom following photodissociation of C4F9I, and also to monitor fluorescence from the iodine molecule at 500 nm to determine if I2 is being produced in the process. Photodissociation is achieved using an XeCl excimer laser with an output wavelength of 308 nm. The XeCl beam is focused into the middle of a cylindrical quartz cell containing the lasant. The laser pulse is detected with a fast risetime photomultiplier tube as it exits the cell. Other aspects of the investigation are discussed.

Cobb, Stephen H.↗

Crystallization Age of NWA 1460 Shergottite: Paradox Revisited

We have determined the Rb-Sr age of basaltic shergottite NWA 1460 to be 312 +/- 3 Ma, and the Sm-Nd age to be 352 +/- 30 Ma. The initial Sr and Nd isotopic compositions of NWA 1460 suggest it is an earlier melting product of a Martian mantle source region similar to those of the Iherzolitic shergottites and basaltic shergottite EETA79001, lithology B. The new ages of NWA 1460 and other recently analyzed Martian meteorites leads us to reexamine the paradox that most of the Martian meteorites appear to be younger from the majority of the Martian surface. This paradox continues to pose a challenge to determining a reliable Martian chronology.

Nyquist, L. E.↗

Sm-Nd and Rb-Sr Ages for MIL 05035: Implications for Surface and Mantle Sources

The Sm-Nd and Rb-Sr ages and also the initial Nd and Sr isotopic compositions of MIL 05035 are the same as those of A-881757. Comparing the radiometric ages of these meteorites to lunar surface ages as modeled from crater size-frequency distributions as well as the TiO2 abundances and initial Sr-isotopic compositions of other basalts places their likely place of origin as within the Australe or Humboldtianum basins. If so, a fundamental west-east lunar asymmetry in compositional and isotopic parameters that likely is due to the PKT is implied.

Nyquist, L. E.↗

Prospects for Chronological Studies of Martian Rocks and Soils

Chronological information about Martian processes comes from two sources: Crater-frequency studies and laboratory studies of Martian meteorites. Each has limitations that could be overcome by studies of returned Martian rocks and soils. Chronology of Martian volcanism: The currently accepted chronology of Martian volcanic surfaces relies on crater counts for different Martian stratigraphic units [1]. However, there is a large inherent uncertainty for intermediate ages near ~2 Ga ago. The effect of differing preferences for Martian cratering chronologies [1] is shown in Fig. 1. Stoeffler and Ryder [2] summarized lunar chronology, upon which Martian cratering chronology is based. Fig. 2 shows a curve fit to their data, and compares to it a corresponding lunar curve from [3]. The radiometric ages of some lunar and Martian meteorites as well as the crater-count delimiters for Martian epochs [4] also are shown for comparison to the craterfrequency curves. Scaling the Stoeffler-Ryder curve by a Mars/Moon factor of 1.55 [5] places Martian shergottite ages into the Early Amazonian to late Hesperian epochs, whereas using the lunar curve of [3] and a Mars/Moon factor ~1 consigns the shergottites to the Middle-to-Late Amazonian, a less probable result. The problem is worsened if a continually decreasing cratering rate since 3 Ga ago is accepted [6]. We prefer the adjusted St ffler-Ryder curve because it gives better agreement with the meteorite ages (Fig.

Nyquist, L. E.↗

Sm-Nd for Norite 78236 and Eucrite Y980318/433: Implications for Planetary and Solar System Processes

Here, we compare Sm-147-Nd-143 and Sm-146-Nd-142 data for lunar norite 78236 to those for approximately 4.54-4.56 Ga old cumulate eucrite Yamato 980318/433 and show that the norite data are compatible with its derivation from an isotopic reservoir similar to that from whence the eucrite pair came. Thus, lunar-like Sm-Nd isotopic systematics are not unique to the Earth-Moon system.

Nyquist, L. E.↗

Concordant Rb-Sr and Sm-Nd Ages for NWA 1460: A 340 Ma Old Basaltic Shergottite Related to Lherzolitic Shergottites

Preliminary Rb-Sr and Sm-Nd ages reported by [1] for the NWA 1460 basaltic shergottite are refined to 336+/-14 Ma and 345+/-21 Ma, respectively. These concordant ages are interpreted as dating a lava flow on the Martian surface. The initial Sr and Nd isotopic compositions of NWA 1460 suggest it is an earlier melting product of a Martian mantle source region similar to those of the lherzolitic shergottites and basaltic shergottite EETA79001, lithology B. We also examine the suggestion that generally "young" ages for other Martian meteorites should be reinterpreted in light of Pb-207/Pb-206 - Pb-204/Pb-206 isotopic systematics [2]. Published U-Pb isotopic data for nakhlites are consistent with ages of approx.1.36 Ga. The UPb isotopic systematics of some Martian shergottites and lherzolites that have been suggested to be approx.4 Ga old [2] are complex. We nevertheless suggest the data are consistent with crystallization ages of approx.173 Ma when variations in the composition of in situ initial Pb as well as extraneous Pb components are considered.

Nyquist, L. E.↗

Mn-53-Cr-53 Systematics of R-Chondrite NWA 753

Chondrules and chondrites are interpreted as objects formed in the early solar system, and it is important to study them in order to elucidate its evolution. Here, we report the study of the Mn-Cr systematics of the R-Chondrite NWA753 and compare the results to other chondrite data. The goal was to determine Cr isotopic and age variations among chondrite groups with different O-isotope signatures. The Mn-53-Cr-53 method as applied to individual chondrules [1] or bulk chondrites [2] is based on the assumption that 53Mn was initially homogeneously distributed in that portion the solar nebula where the chondrules and/or chondrites formed. However, different groups of chondrites formed from regions of different O-isotope compositions. So, different types of chondrites also may have had different initial Mn-53 abundances and/or Cr isotopic compositions. Thus, it is important to determine the Cr isotopic systematics among chondrites from various chondrite groups. We are studying CO-chondrite ALH83108 and Tagish Lake in addition to R-Chondrite NWA753. These meteorites have very distinct O-isotope compositions (Figure 1).

Jogo, K.↗

Chlorine Isotopes: As a Possible Tracer of Fluid/Bio-Activities on Mars and a Progress Report on Chlorine Isotope Analysis by TIMs

Significantly large mass fractionations between chlorine isotopes (Cl-35, Cl-37) have been reported for terrestrial materials including both geological samples and laboratory materials. Also, the chlorine isotopic composition can be used as a tracer for early solar system processes. Moreover, chlorine is ubiquitous on the Martian surface. Typical chlorine abundances in Gusev soils are approx.0.5 %. The global surface average chlorine abundance also is approx.0.5 %. Striking variations among outcrop rocks at Meridiani were reported with some chlorine abundances as high as approx.2%. Characterizing conditions under which chlorine isotopic fractionation may occur is clearly of interest to planetary science. Thus, we have initiated development of a chlorine isotopic analysis technique using TIMS at NASA-JSC. We present here a progress report on the current status of development at JSC and discuss the possible application of chlorine isotopic analysis to Martian meteorites in a search for fluid- and possibly biological activity on Mars.

Nakamura, N.↗

Stable Chlorine Isotope Study: Application to Early Solar System Materials

A significantly large mass fractionation between two stable chlorine isotopes is expected during planetary processes In addition, in view of the isotopic heterogeneity of other light elements, the chlorine isotopes can potentially be used as a tracer for the origins and evolutionary processes of early solar system materials. Due to analytical difficulties, however, current chlorine isotope studies on planetary materials are quite controversial among IRMS (gas source mass spectrometry) and/or TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1-3]. Although a cross-calibration of IRMS and TIMS indicates that both techniques are sufficiently consistent with each other [4], some authors have claimed that the Cl-37/Cl-35 ratio of geological samples obtained by TIMS technique are, in general, misleadingly too high and variable compared to those of IRMS [3]. For example, almost no differences of Cl isotope composition were observed among mantle materials and carbonaceous meteorites by [3]. On the other hand, according to more recent IRMS work [2], significant Cl isotope variations are confirmed for mantle materials. Therefore, additional careful investigation of Cl isotope analyses are now required to confirm real chlorine isotope variations for planetary materials including carbonaceous chondrites [5]. A significantly large mass fractionation between two stable chlorine isotopes is expected during planetary processes In addition, in view of the isotopic heterogeneity of other light elements, the chlorine isotopes can potentially be used as a tracer for the origins and evolutionary processes of early solar system materials. Due to analytical difficulties, however, current chlorine isotope studies on planetary materials are quite controversial among IRMS (gas source mass spectrometry) and/or TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1-3]. Although a cross-calibration of IRMS and TIMS indicates that both techniques are sufficiently consistent with each other [4], some authors have claimed that the 37Cl/35Cl ratio of geological samples obtained by TIMS technique are, in general, misleadingly too high and variable compared to those of IRMS [3]. For eample, almost no differences of Cl isotope composition were observed among mantle materials and carbonaceous meteorites by [3]. On the other hand, according to more recent IRMS work [2], significant Cl isotope variations are confirmed for mantle materials. Therefore, additional careful investigation of Cl isotope analyses are now required to confirm real chlorine isotope variations for planetary materials including carbonaceous chondrites [5]. In order to clarify the stable chlorine isotope features of early solar system materials, we have initiated development of the TIMS technique at NASA JSC applicable to analysis of small amounts of meteoritic and planetary materials. We report here the current status of chlorine isotope analysis at NASA JSC.

Mala,ira. M/↗

Stabile Chlorine Isotope Study of Martian Shergottites and Nakhlites; Whole Rock and Acid Leachates and Residues

We have established a precise analytical technique for stable chlorine isotope measurements of tiny planetary materials by TIMS (Thermal Ionization Mass Spectrometry) [1], for which the results are basically consistent with the IRMS tech-nique (gas source mass spectrometry) [2,3,4]. We present here results for Martian shergottites and nakhlites; whole rocks, HNO3-leachates and residues, and discuss the chlorine isotope evolution of planetary Mars.

Nakamura, N.↗

Sm-Nd and Initial Sr-87/Sr-86 Isotopic Systematics of Asuka 881394 and Cumulate Eucrites Yamato 980318/433 Compared

The Asuka 881394 achondrite contains fossil Al-26 and Mn-53 and has a Pb-206/Pb-207 age of 4566.5 +/- 0.2 Ma, the oldest for an achondrite. Recent re-investigation of A881394 yielded revised initial Sm-146/Sm-144 = (9.1 +/- 1.4) x 10(exp -3), a Sm-147-Nd-143 age of 4525 +/- 58 Ma, a Rb-87-Sr-87 age of 4490 +/- 130 Ma, and initial Sr-87/Sr-86 = 0.698991 +/- 19, respectively. The relatively large uncertainties in the Sm-Nd and Rb-Sr ages are due to disturbances of the isotopic systematics of tridymite and other minor phases. A preliminary value for the Sm-147-Nd-143 age of the Yamato 980318 cumulate eucrite of 4560 +/- 150 Ma was refined in later work to 4567 +/- 24 Ma as reported orally at LPSC 35. Similarly, a preliminary value for Sm-146/Sm-144 = (7.7 +/- 1.2) x 10 (exp -3) was refined to (6.0 +/- 0.3) x 10(exp -3). For Yamato 980433, a Sm-147-Nd-143 age of 4542 +/-42 Ma and Sm-146/Sm-144 = (5.7 +/- 0.5) x 10(exp -3) has been reported. Because these two cumulate eucrites are paired, we consider them to represent one igneous rock and present their combined isotopic data here.

Nyquist, L. E.↗

Mineralogical, Chemical, and Isotopic Heterogeneity in Zagami: Evidence for a Complex Petrogenesis

Textural variations in the shergottite Zagami were initially interpreted as evidence that it formed in a heterogeneous lava flow. Variations in initial Sr-87/Sr-86 ratios between a Coarse Grained (CG) and a Fine Grained (FG) lithology and evidence for more extensive fractionation of the Rb/Sr ratio in a Dark Mottled Lithology (DML) are consistent with such an interpretation. More recently, Niihara et al. and Misawa et al. have reported the mineralogy and Sr-isotopic systematics of an Olivine Rich Lithology (ORL) found in association with the coarse-grained DML lithology in the Kanagawa Zagami specimen [6,7]. Here we call this lithology DML(Ka) to maintain a distinction with DML(USNM) as studied. An Ar-Ar study by Park et al. of a late stage K-rich melt enriched in K2O to approx 7% and intruded into ORL yielded an Ar-Ar age of 202+/0 7 Ma. The present work extends the study of Kanagawa Zagami to Nd-isotopes.

Nyquist, L. E.↗

A Comparison of Anorthositic Lunar Lithologies: Variation on the FAN Theme

Certain anorthositic rocks that are rare in the returned lunar samples have been identified among lunar meteorites. The variety of anorthosites in the Apollo collection also is more varied than is widely recognized. James eta. identified three lithologies in a composite clast o ferroan anorthosite (FAN)-suite rocks in lunar breccia 64435. They further divided all FANs into four subgroups: anorthositic ferroan (AF), mafic magnesian (MM), mafic ferroan (MF), and anorthositic sodic (AS, absent in the 64435 clast). Here we report Sm-Nd isotopic studies of the lithologies present in the 64435 composite clast and compare the new data to our previous data for lunar anorthosites incuding lunar anorthositic meteorites. Mineralogy-petrography, in situ trace element studies, Sr-isotope studies, and Ar-Ar chronology are included, but only the Nd-isotopic studies are currently complete.

Nyquist, L. E.↗

X-Ray Analysis of the Proper Motion and Pulsar Wind Nebula for PSR J1741-2054

We obtained six observations of PSR J1741-2054 using the Chandra ACIS-S detector totaling approx.300 ks. By registering this new epoch of observations to an archival observation taken 3.2 yr earlier using X-ray point sources in the field of view, we have measured the pulsar proper motion at micron = 109 +/- 10 mas yr(exp. -1) in a direction consistent with the symmetry axis of the observed H(alpha) nebula. We investigated the inferred past trajectory of the pulsar but find no compelling association with OB associations in which the progenitor may have originated. We confirm previous measurements of the pulsar spectrum as an absorbed power law with photon index gamma = 2.68 +/- 0.04, plus a blackbody with an emission radius of (4.5(+3.2/-2.5))d(0.38) km, for a DM-estimated distance of 0.38d(0.38) kpc and a temperature of 61.7 +/- 3.0 eV. Emission from the compact nebula is well described by an absorbed power law model with a photon index of gamma = 1.67 +/- 0.06, while the diffuse emission seen as a trail extending northeast of the pulsar shows no evidence of synchrotron cooling. We also applied image deconvolution techniques to search for small-scale structures in the immediate vicinity of the pulsar, but found no conclusive evidence for such structures.

Analysis↗