Engineering topics
Publications and source records attributed to Arnold, James.
A viewgraph describing technologies for entry probes is presented. The topics include: 1) Entry Phase; 2) Descent Phase; 3) Long duration atmospheric observations; 4) Survivability at high temperatures; and 5) Summary.
Materials with improved properties are needed for thermal protection of next generation space vehicles. Sharp leading edges on these vehicles will have to withstand exposure to high temperatures (> 2200 C or 4000 F) and severe thermal cycling in both neutral and oxidizing environments. These extreme conditions will require materials that possess superior oxidation resistance, low creep, and excellent thermal shock properties. This presentation will first discuss the system requirements for thermal protection of advanced space vehicles and then show how they are driving development of new materials systems. The presentation will focus on ultrahigh temperature ceramics (UHTCs) that are promising candidates for such applications. ZrB2 and HfB2 and composites of those ceramics with SiC are two particular families of UHTCs that are currently under development for sharp leading edges. These ceramics are appealing because their melting temperatures are 3245 C (5873 F) for ZrB2 and 3380 C (6116 F) for HfB2 and because they may form protective, oxidation resistant coatings in use. The mechanical properties of the UHTCs are strongly dependent on phase purity and the processing route used to make them, both of which factors are being actively investigated. For example, oxide impurities could form glassy grain boundary phases that soften at high temperatures and make the ceramic susceptible to creep deformation. Results from scanning and transmission electron microscopic studies of the UHTCs have shown how their processing can be improved to give better properties. This presentation will discuss the UHTC characterization results in some detail, focusing particularly on the structure and composition of the ceramic grain boundaries. The presentation will conclude with some remarks on how the properties of these promising UHTCs can be further improved and how they might be made more economically.
In this paper we present results on the stability and lateral resolution capability of carbon nanotube (CNT) scanning probes as applied to atomic force microscopy (AFM). Surface topography images of ultra-thin films (2-5 nm thickness) obtained with AFM are used to illustrate the lateral resolution capability of single-walled carbon nanotube probes. Images of metal films prepared by ion beam sputtering exhibit grain sizes ranging from greater than 10 nm to as small as approximately 2 nm for gold and iridium respectively. In addition, imaging stability and lifetime of multi-walled carbon nanotube scanning probes are studied on a relatively hard surface of silicon nitride (Si3N4). AFM images Of Si3N4 surface collected after more than 15 hrs of continuous scanning show no detectable degradation in lateral resolution. These results indicate the general feasibility of CNT tips and scanning probe microscopy for examining nanometer-scale surface features of deposited metals as well as non-conductive thin films. AFM coupled with CNT tips offers a simple and nondestructive technique for probing a variety of surfaces, and has immense potential as a surface characterization tool in integrated circuit manufacturing.
The binding energy of H to a (10,0) carbon nanotube is calculated at 24, 50, and 100% coverage. Several different bonding configurations are considered for the 50% coverage case. Using the ONIOM (our own n-layered integrated molecular orbital and molecular mechanics) approach, the average C-H bond energy for the most stable 50% coverage and for the 100% coverage are 57.3 and 38.6 kcal/mol, respectively. Considering the size of the bond energy of H2, these values suggest that it will be difficult to achieve 100% atomic H coverage on a (10,0) nanotube.
The (sup 2)Sigma(+) and (sup 2)Pi states of MgO(-) and the (sup 1)Sigma(+), (sup 1)Pi, and (sup 3)Pi states of MgO are studied using the averaged coupled-pair functional (ACPF) approach. The computed spectroscopic constants are in good agreement with the available experimental data. The computed Franck-Condon factors and photodetachment overlaps are compared with experiment.
One of the critical technologies of MHD (Magnetohydrodynamics) bypass scramjet propulsion for space launch and cruise vehicles is MHD acceleration. An experiment in a shock tunnel is described in which MHD acceleration is investigated experimentally. The objectives, the methods used and the preliminary results are described in this paper.
The contribution of the Lamb shift to the atomization energies of some prototype molecules, BF3, AlF3, and GaF3, is estimated by a perturbation procedure. It is found to be in the range of 3-5% of the one-electron scalar relativistic contribution to the atomization energy. The maximum absolute value is 0.2 kcal/mol for GaF3. These sample calculations indicate that the Lamb shift is probably small enough to be neglected for energetics of molecules containing light atoms if the target accuracy is 1 kcal/mol, but for higher accuracy calculations and for molecules containing heavy elements it must be considered.
We have developed computational tools, based on particle codes, for molecular dynamics (MD) simulation of carbon nanotubes (CNT) in aqueous environments. The interaction of CNTs with water is envisioned as a prototype for the design of engineering nano-devices, such as artificial sterocillia and molecular biosensors. Large scale simulations involving thousands of water molecules are possible due to our efficient parallel MD code that takes long range electrostatic interactions into account. Since CNTs can be considered as rolled up sheets of graphite, we expect the CNT-water interaction to be similar to the interaction of graphite with water. However, there are fundamental differences between considering graphite and CNTs, since the curvature of CNTs affects their chemical activity and also since capillary effects play an important role for both dynamic and static behaviour of materials inside CNTs. In recent studies Gordillo and Marti described the hydrogen bond structure as well as time dependent properties of water confined in CNTs. We are presenting results from the development of force fields describing the interaction of CNTs and water based on ab-initio quantum mechanical calculations. Furthermore, our results include both water flows external to CNTs and the behaviour of water nanodroplets inside heated CNTs. In the first case (external flows) the hydrophobic behaviour of CNTs is quantified and we analyze structural properties of water in the vicinity of CNTs with diagnostics such as hydrogen bond distribution, water dipole orientation and radial distribution functions. The presence of water leads to attractive forces between CNTs as a result of their hydrophobicity. Through extensive simulations we quantify these attractive forces in terms of the number and separation of the CNT. Results of our simulations involving arrays of CNTs indicate that these exhibit a hydrophobic behaviour that leads to self-organising structures capable of trapping water clusters. In the second case (internal flows) we study the behaviour of water droplets confined inside CNTs. Constant temperature simulations allow us to capture structural properties such as the contact angles and density profiles of the equilibrated drops. By heating and subsequently cooling of the CNT, we are able to measure the evaporation and the condensation rate of the entrapped water.
During oxide etch processes, buildup of fluorocarbon residues on reactor sidewalks can cause to drift and will necessitate time for conditioning and cleaning of the reactor. Various measurements in CF4 and Ar plasmas are made in an attempt to identify a metric able to indicate the chamber condition. Mass spectrometry and a Langmuir probe shows that the buildup of fluorocarbon films on the reactor surface causes a decrease in plasma floating potential, plasma potential, and ion energy in argon plasmas. This change in floating potential is also observed in CF4 plasma operation, and occurs primarily during the first hour and a half of plasma operation. A slight rise in electron density is also observed in the argon plasmas. Because the change is seen in an argon plasma, it is indicative of altered physical, not chemical, plasma-surface interactions. Specifically, the insulating films deposited on metal surfaces alter the electromagnetic fields seen by the plasma, affecting various parameters including the floating potential and electron density. An impedance probe placed on the inductive coil shows a slight reduction in plasma impedance due to this rising electron density. The optical emission of several species, including CF, C2, atomic Si and atomic C, is also monitored for changes in density resulting from the buildup of film on the chamber wall. Changes in the optical emission spectrum are comparable to the noise levels in their measurement.
Thermal protection materials and systems (IRS) are used to protect spacecraft during reentry into Earth's atmosphere or entry into planetary atmospheres. As such, these materials are subject to severe environments with high heat fluxes and rapid heating. Catalytic effects can increase the temperatures substantially. These materials are also subject to impact damage from micrometeorites or other debris during ascent, orbit, and descent, and thus must be able to withstand damage and to function following damage. Thermal protection materials and coatings used in reusable launch vehicles will be reviewed, including the needs and directions for new materials to enable new missions that require faster turnaround and much greater reusability. The role of ablative materials for use in high heat flux environments, especially for non-reusable applications and upcoming planetary missions, will be discussed. New thermal protection system materials may enable the use of sharp nose caps and leading edges on future reusable space transportation vehicles. Vehicles employing this new technology would have significant increases in maneuverability and out-of-orbit cross range compared to current vehicles, leading to increased mission safety in the event of the need to abort during ascent or from orbit. Ultrahigh temperature ceramics, a family of materials based on HfB2 and ZrB2 with SiC, will be discussed. The development, mechanical and thermal properties, and uses of these materials will be reviewed.
The Mars Climate Orbiter failed to achieve Mars orbit on September 23, 1999. On December 3, 1999, Mars Polar Lander and two Deep Space 2 microprobes failed. As a result, the NASA Administrator established the Mars Program Independent Assessment Team (MPIAT) with the following charter: 1) Review and analyze successes and failures of recent Mars and Deep Space Missions which include: a) Mars Global Surveyor, b) Mars Climate Orbiter, c) Pathfinder, d) Mars Polar Lander, e) Deep Space 1, and f) Deep Space 2; 2) Examine the relationship between and among, NASA Jet Propulsion Laboratory (JPL), California Institute of Technology (Caltech), NASA Headquarters, and industry partners; 3) Assess effectiveness of involvement of scientists; 4) Identify lessons learned from successes and failures; 5) Review revised Mars Surveyor Program to assure lessons learned are utilized; 6) Oversee Mars Polar Lander and Deep Space 2 failure reviews; and 7) Complete by March 15, 2000. In-depth reviews were conducted at NASA Headquarters, JPL, and Lockheed Martin Astronautics (LMA). Structured reviews, informal sessions with numerous Mars Program participants, and extensive debate and discussion within the MPIAT establish the basis for this report. The review process began on January 7, 2000, and concluded with a briefing to the NASA Administrator on March 14, 2000. This report represents the integrated views of the members of the MPIAT who are identified in the appendix. In total, three related reports have been produced: a summary report, this report entitled "Mars Program Independent Assessment Team Report," and the "Report on the Loss of the Mars Polar Lander and Deep Space 2 Missions".
We study the energetics of CH2O + NH3-Yields CH2NH + H2O in the gas phase at the B3LYP and CCSD(T)levels. This reaction is shown to have a sizeable barrier. Ionization of NH3 reduces the barrier to about 5 kcal/mol. We also show that in water, a proton catalyzed mechanism yields no barriers in excess of the reaction endothermicity. Since this reaction has been proposed as one of the steps in interstellar synthesis of glycine, the simplest amino acid, this work suggests that the formation of amino acids is occurring in and/or on interstellar water ice grains, and not in the gas phase.
The combination of density functional theory (DFT) frequencies and infrared (IR) intensities and experimental spectra is a very powerful tool in the identification of molecules and ions. The computed and measured isotopic ratios make the identification much more secure than frequencies and intensities alone. This will be illustrated using several examples, such as Mn(CO)n and Mn(CO)n-. The accuracy of DFT metal-ligand bond energies will also be discussed.
Heats of formation for cyclic C4F8 and C4F8+ are determined at the G3MP2 level. The several decomposition pathways are investigated. The calculations confirm that C4F8+ rearranges and its decomposition is responsible for both the C2F4+ and C3F5+ species observed in experiment. The heats of formation are presented for C4Fn and C4Fn+, n = 4-8.
The dissociation of WF6 and the related singly-charged cations and anions into the lower fluorides and fluorine atoms has been investigated theoretically using density functional theory (B3LYP) and relativistic effective core potentials, with estimates of spin-orbit effects included using a simple model. The inclusion of spin-orbit is essential for a correct description of the thermochemistry. The total atomization energy of the neutral and anionic WF6 is reproduced to within 25 kcal/mol, but comparison of individual bond dissociation energies with available experimental data shows discrepancies of up to 10 kcal/mol. The results are nevertheless useful to help resolve discrepancies in experimental data and provide estimates of missing data.
It is now possible to compute IR (infrared) spectra of large molecules with an accuracy of 30 per cm, or better, using density function theory. This is true for cations, anions, and neutrals. Thus it possible to generate synthetic IR spectra that can help interpret experimental spectra and fill in for missing experimental data. These synthetic spectra can be used as input into interstellar models. In addition to IR spectra, it is possible to compute energetic properties to help understand which molecules can be formed in the interstellar environment.
The ground and low-lying electronic states of CaN2(+) are studied at several levels of theory. The results for the X(sup 2)Sigma(+) state and the excited (2)(sup 2)Pi state, arising from occupying the Ca 4p orbital, are in good agreement with experiment. The analogous states of Ca(N2)2(+) are studied using the same theoretical approaches, and predictions are made as to the changes caused by the addition of the second N2 ligand.
The addition of tight functions to sulphur and extrapolation to the complete basis set limit are required to obtain accurate atomization energies. Six different extrapolation procedures are tried. The best atomization energies come from the series of basis sets that yield the most consistent results for all extrapolation techniques. In the variable alpha approach, alpha values larger than 4.5 or smaller than 3, appear to suggest that the extrapolation may not be reliable. It does not appear possible to determine a reliable basis set series using only the triple and quadruple zeta based sets. The scalar relativistic effects reduce the atomization of SO and SO2 by 0.34 and 0.81 kcal/mol, respectively, and clearly must be accounted for if a highly accurate atomization energy is to be computed. The magnitude of the core-valence (CV) contribution to the atomization is affected by missing diffuse valence functions. The CV contribution is much more stable if basis set superposition errors are accounted for. A similar study of SF, SF(+), and SF6 shows that the best family of basis sets varies with the nature of the S bonding.