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At least 289 records · Page 16

Effect of barrier height on friction behavior of the semiconductors silicon and gallium arsenide in contact with pure metals

Friction experiments were conducted for the semiconductors silicon and gallium arsenide in contact with pure metals. Polycrystalline titanium, tantalum, nickel, palladium, and platinum were made to contact a single crystal silicon (111) surface. Indium, nickel, copper, and silver were made to contact a single crystal gallium arsenide (100) surface. Sliding was conducted both in room air and in a vacuum of 10 to the minus 9th power torr. The friction of semiconductors in contact with metals depended on a Schottky barrier height formed at the metal semiconductor interface. Metals with a higher barrier height on semiconductors gave lower friction. The effect of the barrier height on friction behavior for argon sputtered cleaned surfaces in vacuum was more specific than that for the surfaces containing films in room air. With a silicon surface sliding on titanium, many silicon particles back transferred. In contrast, a large quantity of indium transferred to the gallium arsenide surface.

Mishina, H.↗

Observation of surface states on gold films by electron tunneling spectroscopy

It is pointed out that inelastic electron tunneling spectroscopy (IETS) is a useful technique for the study of vibrational modes of molecules adsorbed on the surface of the insulating layer in a metal-insulator-metal tunnel junction. A detailed study of electron tunneling in aluminum-aluminum oxide-gold (Al-Al2O3-Au) tunnel junctions has been conducted with an overall goal of exploring possible mechanisms in such a thin film device useful for chemical sensing. For an understanding of the electronic effects in the presence of chemicals in a junction, the electronic surface properties of the metallic films in a clean tunnel junction must be established. The present investigation is concerned with room temperature observations of electronic states on the surface of highly oriented gold film in Al-Al2O3-Au junctions.

Lambe, J.↗

Preliminary Investigation of the Effect of Surface Treatment on the Strength of a Titanium Carbide - 30 Percent Nickel Base Cermet

Specimens of a nickel-bonded titanium carbide cermet were given the following surface treatments: (1) grinding, (2) lapping, (3) blast cleaning, (4) acid roughening, (5) oxidizing, and (6) oxidizing and refinishing. Room-temperature modulus-of-rupture and impact strength varied with the different surface treatments. Considerable strength losses resulted from the following treatments: (1) oxidation at 1600 F for 100 hours, (2) acid roughening, and (3) severe grinding with 60-grit silicon carbide abrasive. The strength loss after oxidation was partially recovered by grit blasting or diamond grinding.

MATERIALS, PROPERTIES - FLEXURE↗

Addressing Issues with Working Memory in Video Object Segmentation

Contemporary state-of-the-art video object segmentation (VOS) models compare incoming unannotated images to a history of image-mask relations via affinity or cross-attention to predict object masks. We refer to the internal memory state of the initial image-mask pair and past image-masks as a working memory buffer. While the current state of the art models perform very well on clean video data, their reliance on a working memory of previous frames leaves room for error. Affinity-based algorithms include the inductive bias that there is temporal continuity between consecutive frames. To account for inconsistent camera views of the desired object, working memory models need an algorithmic modification that regulates the memory updates and avoid writing irrelevant frames into working memory. A simple algorithmic change is proposed that can be applied to any existing working memory-based VOS model to improve performance on inconsistent views, such as sudden camera cuts, frame interjections, and extreme context changes. The resulting model performances show significant improvement on video data with these frame interjections over the same model without the algorithmic addition. Our contribution is a simple decision function that determines whether working memory should be updated based on the detection of sudden, extreme changes and the assumption that the object is no longer in frame. By implementing algorithmic changes, such as this, we can increase the real-world applicability of current VOS models.

97 MATHEMATICS AND COMPUTING↗

Sample Acquisition and Analytical Chemistry Challenges to Verifying Compliance to Aviators Breathing Oxygen (ABO) Purity Specification

NASA has been developing and testing two different types of oxygen separation systems. One type of oxygen separation system uses pressure swing technology, the other type uses a solid electrolyte electrochemical oxygen separation cell. Both development systems have been subjected to long term testing, and performance testing under a variety of environmental and operational conditions. Testing these two systems revealed that measuring the product purity of oxygen, and determining if an oxygen separation device meets Aviator's Breathing Oxygen (ABO) specifications is a subtle and sometimes difficult analytical chemistry job. Verifying product purity of cryogenically produced oxygen presents a different set of analytical chemistry challenges. This presentation will describe some of the sample acquisition and analytical chemistry challenges presented by verifying oxygen produced by an oxygen separator - and verifying oxygen produced by cryogenic separation processes. The primary contaminant that causes gas samples to fail to meet ABO requirements is water. The maximum amount of water vapor allowed is 7 ppmv. The principal challenge of verifying oxygen produced by an oxygen separator is that it is produced relatively slowly, and at comparatively low temperatures. A short term failure that occurs for just a few minutes in the course of a 1 week run could cause an entire tank to be rejected. Continuous monitoring of oxygen purity and water vapor could identify problems as soon as they occur. Long term oxygen separator tests were instrumented with an oxygen analyzer and with an hygrometer: a GE Moisture Monitor Series 35. This hygrometer uses an aluminum oxide sensor. The user's manual does not report this, but long term exposure to pure oxygen causes the aluminum oxide sensor head to bias dry. Oxygen product that exceeded the 7 ppm specification was improperly accepted, because the sensor had biased. The bias is permanent - exposure to air does not cause the sensor to return to its original response - but the bias can be accounted for by recalibrating the sensor. After this issue was found, continuous measurements of water vapor in the oxygen product were made using an FTIR. The FTIR cell is relatively large, so response time is slow - but moisture measurements were repeatable and accurate. Verifying ABO compliance for oxygen produced by commercial cryogenic processes has a different set of sample acquisition and analytical chemistry challenges. Customers want analytical chemists to conserve as much as possible. Hygrometers are not exposed to hours of continuous flow of oxygen, so they don't bias, but small amounts of contamination in valves can cause a "fail". K bottles are periodically cleaned and recertified - after cleaning residual moisture can cause a "fail". Operators let bottle pressure drop to room pressure, introduce outside air into the bottle, and the subsequent fill will "fail". Outside storage of K‐bottles has allowed enough in‐leakage, so contents will "fail".

Graf, John↗

Adhesion and friction of iron and gold in contact with elemental semiconductors

Adhesion and friction experiments were conducted with single crystals of iron and gold in contact with single crystals of germanium and silicon. Surfaces were examined in the sputter cleaned state and in the presence of oxygen and a lubricant. All experiments were conducted at room temperature with loads of 1 to 50 grams, and sliding friction was at a sliding velocity of 0.7 mm/min. Results indicate that the friction nature of metals in contact with semiconductors is sensitive to orientation, that strong adhesion of metals to both germanium and silicon occurs, and that friction is lower with silicon than with germanium for the same orientation. Surface effects are highly sensitive to environment. Silicon, for example, behaves in an entirely brittle manner in the clean state, but in the presence of a lubricant the surface deforms plastically.

Buckley, D. H.↗

Probing the surface chemistry for reverse water gas shift reaction on Pt(1 1 1) using ambient pressure X-ray photoelectron spectroscopy

Using ambient pressure XPS (APXPS), we explored carbon dioxide (CO 2 ) adsorption and CO 2 hydrogenation on Pt(1 1 1) single crystal surface to observe the activation of CO 2 and the subsequent reaction mechanism. In pure CO 2 , we observed CO adsorbates and adsorbed oxygen on Pt(1 1 1) derived from CO 2 dissociation at room temperature. The introduction of H 2 (at a pressure ratio of 1:1 (H 2 :CO 2 )) increased the production of CO across all temperatures by facilitating the removal of surface oxygen. As a consequence, the surface could expose sites that could then be utilized for producing CO. Under these conditions, the reverse water–gas shift (RWGS) reaction was observed starting at 300 °C. At higher H 2 partial pressure (10:1 (H 2 :CO 2 )), the RWGS reaction initiated at a lower temperature of 200 °C and continued to enhance the conversion of CO 2 with increasing temperatures. Our results revealed that CO 2 was activated on a clean Pt(1 1 1) surface through the dissociation mechanism to form adsorbed CO and O at room temperature and at elevated temperatures. Introducing H 2 facilitated the RWGS as adsorbed oxygen was consumed continuously to form H 2 O, and adsorbed CO desorbed from the surface at elevated temperatures. This work clearly provides direct experimental evidence for the surface chemistry of CO 2 dissociation and demonstrates how hydrogen impacts the RWGS reaction on a platinum surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Miniature, Lightweight, One-Time-Opening Valve

The figure depicts the main parts of a prototype miniature, lightweight, onetime- opening valve. Like some other miniature one-time-opening valves reported in previous issues of NASA Tech Briefs, this valve is opened by melting a material that blocks the flow path. This valve is designed to remain closed at some temperature between room temperature and cryogenic temperature until the time of opening. The prototype valve includes a 1/8-in. (3-mm) aluminum tube, one end of which is plugged with a solder comprising about 37 weight percent of lead and 63 weight percent of tin. The tube and the solder both have a coefficient of thermal expansion of 23 micron/m-K at room temperature. Before plugging, the interior surface of the plug end of the tube is cleaned with a commercial flux paste developed specifically for preparing aluminum for bonding with lead/tin solder. The solder is then melted into the cleaned end of the tube, forming the plug. In a test, the plugged tube was pressurized to 1,000 psi (6.9 MPa) with helium and leak-tested. It was then cooled to a temperature of 77 K (about 196 C) and again leak-tested at the same pressure. Finally, at a lower pressure, the plugged end of the tube was heated to about 200 C (the melting temperature of the solder is 183 C), causing the solder plug to be ejected (see figure). It has been estimated that in a subsequent version of the valve, the plug could be melted by electrical heating, using a nichrome wire having a mass of only 10 g.

Jones, Jack↗

Mechanisms of Oxide Formation in the Self-Reacting Friction Stir Weld Process

The initial objective of this study was to evaluate the effect of an extended delay time between preweld cleaning and the completion of a self-reacting friction stir welding (SRFSW) process on the resulting quality of various thickness panels of AA2219-T87. The current NASA standard specifies no more than a 48 hour delay between preweld cleaning and actual welding. The concern is whether increasing the cleaning delay time results in development of the residual oxide defect (ROD) in SRFSW. This concern emanates from the possibility of increased time correlating with increased oxide layer thickness on the faying surfaces. Oxide content on the faying surfaces has been reported to correlate with the occurrence of the ROD which reduces mechanical properties. When the SRFSW process was first adopted by the NASA Marshall Space Flight Center (MSFC), unexpected low tensile values that resulted were attributed to oxides within the weld that appeared to follow the former faying surface contours. Mitigation of the ROD was achieved through a combination of modifications to the processing parameters, tool designs, and incorporation of a weld seam offset. Two operations are involved in preweld cleaning: the first is removal of oil and grease, and the second is removal of surface oxides. In arc welding, improper cleaning of the faying surfaces of aluminum welded joints can increase the sensitivity toward development of defects. As the aluminum is locally melted, these contaminants contribute toward the development of porosity, inclusions, entrapped oxides, and other discontinuities which can degrade the strength of the weld joint. For weldment of large structures, the weld joint is typically cleaned, fit-up, and tack welded prior to the final full penetration welding pass. Because of the stringent joint fit-up requirements for mismatch and peaking for launch vehicle structures, the joint fit-up can sometimes contribute to lengthy delays between cleaning and tack welding, especially for circumferential weld joints on large diameter components. When the conventional friction stir welding (CFSW) process was introduced at the NASA MSFC, there was no procedure for cleaning prior to the solid-state joining process. As the process expanded to include SRFSW, preparation of the faying, crown, and root surfaces were implemented to overcome the ROD. Although the solid-state process is not expected to reach temperatures high enough for dissociation of the native oxide layer, concern remained regarding the redeposition of the native oxide layer within the stir zone. NASA has previously established the allowable time at 48 hours between preweld cleaning and a SRFSW process. The effect of potential 2 contamination resulting from an extended delay to 188 hours was subsequently evaluated for SRFSWs using tensile testing and metallographic imaging. Tensile specimens were tested at room temperature (RT), and at cryogenic conditions of liquid nitrogen (LN2) and liquid hydrogen. No detrimental effect on weld quality, as determined by weld strength, was reported for cleaning delays of 48, 120, 168, 240 or 288 hours. While no trends were established in this study, which extended the delay from 48 to 188 hours, there were a few outliers in terms of ultimate tensile strength (UTS). According to M. Fisher's 2014 Boeing Company Memo no. EYBF-MAF-14-029, all outliers were above the minimum acceptance criteria, but out of family with respect to the average values. As the robustness and reliability of any process ultimately depends on the average values as well as the outliers, an understanding of the cause of these outliers will ultimately improve the process. This report examines those outliers and their possible causes.

Schneider, J. A.↗

Reaction of sulfur dioxide with modified 440C, studied by Auger electron spectroscopy and depth profiling

Auger electron spectroscopy and sputtering were used to study the interaction of SO2 with modified 440C, which is a nominally 77-wt%-Fe, 14-wt%-Cr, and 4-wt%-Mo bearing steel with C, S, Si, Ni, V, P, and Mn making up the balance. The sample was polycrystalline. Three temperatures were used: room temperature, 500 C, and 600 C. The reaction time was varied from 30 minutes to 2 hours. A surface cleaned of oxides was the starting point for each reaction. For reactions at 500 C, the major constituents Cr, O, Fe, and S were present in the surface film. At 600 C, the principal constituents of the film were Cr, O, and S with no Fe present. Therefore, a transition in film composition occurred between 500 and 600 C. Oxides were the primary constituents of the films at both temperatures. Room-temperature reactions indicated that SO2 adsorbed dissociatively, with approximately equal quantities of S and O on the surface. For the same reaction time (1 hr) and pressure, a strong temperature dependence of film thickness was observed. The film formed at 600 C was approximately seven times thicker than that formed at 500 C.

Ferrante, J.↗

Clean Assembly of Genesis Collector Canister for Flight: Lessons for Planetary Sample Return

Measurement of solar composition in the Genesis collectors requires not only high sensitivity but very low blanks; thus, very strict collector contamination minimization was required beginning with mission planning and continuing through hardware design, fabrication, assembly and testing. Genesis started with clean collectors and kept them clean inside of a canister. The mounting hardware and container for the clean collectors were designed to be cleanable, with access to all surfaces for cleaning. Major structural components were made of aluminum and cleaned with megasonically energized ultrapure water (UPW). The UPW purity was >18 M resistivity. Although aluminum is relatively difficult to clean, the Genesis protocol achieved level 25 and level 50 cleanliness on large structural parts; however, the experience suggests that surface treatments may be helpful on future missions. All cleaning was performed in an ISO Class 4 (Class 10) cleanroom immediately adjacent to an ISO Class 4 assembly room; thus, no plastic packaging was required for transport. Persons assembling the canister were totally enclosed in cleanroom suits with face shield and HEPA filter exhaust from suit. Interior canister materials, including fasteners, were installed, untouched by gloves, using tweezers and other stainless steel tools. Sealants/lubricants were not exposed inside the canister, but vented to the exterior and applied in extremely small amounts using special tools. The canister was closed in ISO Class 4, not to be opened until on station at Earth-Sun L1. Throughout the cleaning and assembly, coupons of reference materials that were cleaned at the same time as the flight hardware were archived for future reference and blanks. Likewise reference collectors were archived. Post-mission analysis of collectors has made use of these archived reference materials.

Allton, J. H.↗

Exploring Local Vibrational Structure in Protein-Bound Chlorophyll a: Isotope-Enrichment Experiments and Electrostatic Analysis

Local chlorophyll (Chl) vibrations play an essential role in biological photosynthesis by facilitating rapid energy transfer between pigments. In research studies, they also provide a useful spectroscopic probe of the local protein environment that surrounds each pigment. However, measuring the complete vibrational absorption spectrum of a protein-bound Chl molecule is much more difficult than, for example, Chl in neat solvent due to overlap with protein vibrations that typically drown out Chl vibrational features. Resonance Raman and fluorescence spectroscopies provide a way around this problem for Franck–Condon active vibrations, but these often rely on cryogenic measurement conditions and fail to capture vibrational signatures from, e.g., ester-group vibrations that lack coupling to a convenient electronic transition. In the present contribution, we use 13 C-enrichment of the protein backbone to shift protein background signals to lower frequency, providing a largely clean spectral window in which to study local Chl a C═O stretch modes. A room-temperature absorption spectrum for Chl a in the water-soluble chlorophyll protein (WSCP) of Lepidium virginicum is thus extracted as a difference between protein-plus-pigment and protein-only vibrational spectra. Excellent agreement in the molecular fingerprint region with the vibrational spectrum of Chl a in organic solvents confirms that the resulting spectrum represents the response of the protein-bound Chl a molecule. Furthermore, the ester group resonance is observed to shift in response to the S53P mutation that eliminates a 17 3 ester group hydrogen bond from the protein environment. Finally, we analyze these experimental results using MD-based electrostatic analysis, finding that electric-field mapping at the C atom of the ester group provides a satisfactory explanation for the observed frequency shifts between organic solvent and protein environment. MD analysis further suggests that a red-shifted ester peak observed experimentally for the S53P mutant results from solvation of the 17 3 Chl ester group due increase water penetration into the Chl-binding pocket relative to wild-type WSCP. Here, we anticipate that these results will prove useful both for benchmarking future simulation work and as a reference for interpreting Chl vibrational spectra as a probe of pigment–protein interactions.

14 SOLAR ENERGY↗

Superlattice reflection signatures of the insulator–metal transition in V 3 O 5 thin films

Nanoelectronic systems that are inspired by the brain are increasingly looking to insulator–metal transition (IMT) materials as they can mimic the response characteristics of neurons to temperature changes so that these can be used in robotic and computational applications. V 3 O 5 has an insulator–metal transition at ∼430 or ∼80 K higher than VO 2 and provides a unique high-temperature opportunity for these types of applications. Here, in this work, we track the structural evolution of V 3 O 5 thin films across the IMT through conventional selected-area electron diffraction (SAED) and four-dimensional scanning TEM (4D-STEM), correlated with temperature-dependent resistance measurements. SAED patterns show reversible evidence of superlattice reflections associated with the IMT—present below T IMT and absent above it—consistent with the accompanying drop in resistance. At room temperature, nanobeam electron diffraction patterns further reveal three local configurations: (i) type I regions with clean patterns lacking superlattice reflections and spot splitting; (ii) type II regions exhibiting rows of superlattice reflections and split spots indicative of crystallographic variants; and (iii) type III regions with negligible superlattice reflections but larger spot splitting suggestive of overlapping domains of insulating and conducting phases likely driven by local lattice distortions. Upon heating, the superlattice reflections disappear between 413 and 453 K, concurrent with the resistance drop at T IMT , consistent with the emergence of a conducting phase. The overall diffraction geometry remains essentially unchanged up to 573 K, implying that relative domain orientations persist through the transition. These observations reveal nanoscale structural heterogeneity in V 3 O 5 thin films across the IMT and inform operation in regimes where mixed-phase textures are expected. A plausible indexing framework rationalizing the observed geometries is presented in the Discussion section, alongside its limitations and alternative interpretations.

25 ENERGY STORAGE↗

The surface structure of titanium and its interaction with bromine and chlorine

The surface structure and composition of titanium have been studied by electron diffraction and Auger electron spectroscopy in the temperature range 25 to 850 C. Atomically clean, well-defined Ti surfaces were obtained by a combination of argon ion sputtering and thermal treatment at 700 to 800 C. A series of surface superstructures was observed as the crystal temperature was gradually decreased. The development of the superstructures is best explained as due to surface reconstruction as a result of surface relaxation. The interaction of bromine and chlorine vapors with clean Ti surfaces was investigated in the temperature range 25 to 500 C. Bromine exposure at room temperature gave rise to an amorphous surface layer, which on annealing transformed into an epitaxial TiBr2 structure. Chlorine interaction resulted in the formation of an epitaxial TiCl3 on both cold and hot Ti surfaces. Surface impurities inhibited the chemical interaction process on the Ti surface.

Khan, I. H.↗

Drastic reduction of adsorption of CO and H2 on (111)-type Pd layers

Clean surfaces of (111)-type Pd layers, grown from the vapor phase on Mo(110) at room temperature, were used to study the adsorption of CO and H2 by temperature-programmed desorption, Auger electron spectroscopy, and low-energy electron diffraction. Mild annealing of the as-grown layers during a single desorption cycle (to about 600 K) drastically reduces the adsorption for both adsorbates. Low-dose argon-ion bombardment introduces surface imperfections which restore a high adsorption probability. The results are interpreted in terms of particular (111)-type surface structures that persist tp layer thicknesses of about four monolayers; the results raise questions with respect to the surface structure of supported thin epitaxial islands and particles of Pd and possibly also with respect to conventional methods of preparing bulk surfaces of Pd for adsorption studies.

Poppa, H.↗

In Situ Monitoring of Non-Thermal Plasma Cleaning of Surfactant Encapsulated Nanoparticles

Surfactants are widely used in the synthesis of nanoparticles, as they have a remarkable ability to direct their growth to obtain well-defined shapes and sizes. However, their post-synthesis removal is a challenge, and the methods used often result in morphological changes that defeat the purpose of the initial controlled growth. Moreover, after the removal of surfactants, the highly active surfaces of nanomaterials may undergo structural reconstruction by exposure to a different environment. Thus, ex situ characterization after air exposure may not reflect the effect of the cleaning methods. Here, combining X-ray photoelectron spectroscopy, in situ infrared reflection absorption spectroscopy, and environmental transmission electron microscopy measurements with CO probe experiments, we investigated different surfactant-removal methods to produce clean metallic Pt nanoparticles from surfactant-encapsulated ones. It was demonstrated that both ultraviolet-ozone (UV-ozone) treatment and room temperature O2 plasma treatment led to the formation of Pt oxides on the surface after the removal of the surfactant. On the other hand, when H2 was used for plasma treatment, both the Pt0 oxidation state and nanoparticle size distribution were preserved. In addition, H2 plasma treatment can reduce Pt oxides after O2-based treatments, resulting in metallic nanoparticles with clean surfaces. These findings provide a better understanding of the various options for surfactant removal from metal nanoparticles and point toward non-thermal plasmas as the best route if the integrity of the nanoparticle needs to be preserved.

36 MATERIALS SCIENCE↗

Scanning tunneling spectroscopy of surface-oxidized Gallium-stabilized δ -phase plutonium

Here, the first contiguous experimental scanning tunneling spectroscopy (STS) measurements of the electronic structure of a plutonium (Pu) surface are presented and compared to current theoretical results. The experiments took place under UHV conditions, for which Pu is known to retain a native surface oxide. The STS data shows that no band gap is observable at room temperature. Theoretical calculations predict that bulk Pu oxides are semiconductors, but the spectral results for the cleaned Pu surface native oxide under UHV conditions could be better characterized as that of a semimetal.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Molecular beam homoepitaxy of N-polar AlN: Enabling role of aluminum-assisted surface cleaning

N-polar aluminum nitride (AlN) is an important building block for next-generation high-power radio frequency electronics. We report successful homoepitaxial growth of N-polar AlN by molecular beam epitaxy (MBE) on large-area, cost-effective N-polar AlN templates. Direct growth without any in situ surface cleaning leads to films with inverted Al polarity. It is found that Al-assisted cleaning before growth enables the epitaxial film to maintain N-polarity. The grown N-polar AlN epilayer with its smooth, pit-free surface duplicates the structural quality of the substrate, as evidenced by a clean and smooth growth interface with no noticeable extended defects generation. Near band-edge photoluminescence peaks are observed at room temperature on samples with MBE-grown layers but not on the bare AlN templates, implying the suppression of nonradiative recombination centers in the epitaxial N-polar AlN.

42 ENGINEERING↗