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Controlled Contamination of Epoxy Composites with PDMS and Removal by Laser Ablation

Surface preparation is critical to the performance of adhesively bonded composites. During manufacturing, minute quantities of mold release compounds are inevitably deposited on faying surfaces and may compromise bond performance. To ensure safety, mechanical fasteners and other crack arrest features must be installed in the bondlines of primary structures, which negates some advantages of adhesively bonded construction. Laser ablation is an automated, repeatable, and scalable process with high potential for the surface preparation of metals and composites in critical applications such as primary airframe structures. In this study, laser ablation is evaluated on composite surfaces for the removal of polydimethylsiloxane (PDMS), a common mold release material. Composite panels were contaminated uniformly with PDMS film thicknesses as low as 6.0 nm as measured by variable angle spectroscopic ellipsometry. Bond performance was assessed by mechanical testing using a 250 F cure, epoxy adhesive and compared with pre-bond surface inspection results. Water contact angle, optically stimulated electron emission, and laser induced breakdown spectroscopy were used to characterize contaminated and laser ablated surfaces. The failure mode obtained from double cantilever beam tests correlated well with surface characterization data. The test results indicated that even low levels of PDMS were not completely removed by laser ablation.

Palmieri, Frank↗

Optical and interfacial electronic properties of diamond-like carbon films

Hard, semitransparent carbon films were prepared on oriented polished crystal wafers of silicon, indium phosphide and gallium arsenide, as well as on KBr and quartz. Properties of the films were determined using IR and visible absorption spectrocopy, ellipsometry, conductance-capacitance spectroscopy and alpha particle-proton recoil spectroscopy. Preparation techniques include RF plasma decomposition of methane (and other hydrocarbons), ion beam sputtering, and dual-ion-beam sputter deposition. Optical energy band gaps as large as 2.7 eV and extinction coefficients lower than 0.1 at long wavelengths are found. Electronic state densities at the interface with silicon as low as 10 to the 10th states/eV sq cm per were found.

Woollam, J. A.↗

Laser induced OMCVD growth of AlGaAs on GaAs

A major factor limiting the efficiency of the GaAs-GaAlAs solar cell is the rate of recombination at the GaAs-AlGaAs interface. Evidence has been previously reported which indicates that recombination at this interface can be greatly reduced if the AlGaAs layer is grown at lower than normal temperatures. The authors examine the epitaxial growth of AlGaAs on GaAs using a horizontal OMCVD reactor and an excimer laser operating in the UV (lambda = 193 nm) region. The growth temperatures were 450 and 500 C. The laser beam was utilized in two orientations: 75 deg angle of incidence and parallel to the substrate. Film composition and structure were determined by Auger electron spectroscopy (AES) and transmission electron microscopy (TEM). Auger analysis of epilayers grown at 500 C with the laser impinging show no carbon or oxygen contamination of the epitaxial layers or interfaces. TEM diffraction patterns of these same epilayers exhibit single crystal (100) zone axis patterns.

Wilt, David M.↗

Auger and ESCA analysis

X-ray photoelectron spectroscopy (XPS or ESCA) and Auger electron spectroscopy (AES) techniques are discussed. The XPS instrument is a Perkin-Elmer 5400 system which provides both elemental and chemical state information without restriction on the type of material that can be analyzed. The AES instrument is a Kratos Analytical XSAM 800 system. AES uses a beam of high energy electrons as a surface probe. Following electronic rearrangements within excited atoms by this probe, Auger electrons characteristic of each element present are emitted from the sample. Specific examples of analytic techniques and results are presented.

Gregory, John C.↗

Electron spectroscopy of the diamond surface

The diamond surface is studied by ionization loss spectroscopy and Auger electron spectroscopy. For surfaces heated to temperatures not exceeding 900 C, the band gap was found to be devoid of empty states in the absence of electron beam effects. The incident electron beam generates empty states in the band gap and loss of structure in the valence band for these surfaces. A cross section of 1.4 x 10 to the -19th sq cm was obtained for this effect. For surfaces heated to temperatures exceeding 900 C the spectra were identical to those from surfaces modified by the electron beam. The diamond surface undergoes a thermal conversion in its electronic structure at about 900 C.

Pepper, S. V.↗

Zircon, Baddeleyite, and Reidite Found in Ries Crater Suevite

Introduction: Impact events can generate superheated impact melts and even vapor [1]. In the past decade, evidence of the high temperatures and high pressures of the impact process has been found in the impact melt from terrestrial craters (e.g., Mistastin Lake [2], Meteor Crater [3]) and even on the Moon [4–5]. Often, these studies involve zircon or zirconium-bearing phases. Zircon is a particularly useful mineral, due to its robustness and durability against weathering. It is used principally for chronology, but it has a multitude of geologic applications, including geothermometry and fingerprinting magma sources. Here we focus on its capability of recording impact conditions. Grains of zircon (ZrSiO4) are converted at high temperature and/or pressure during an impact event to reidite (a high-pressure polymorph of ZrSiO4) or to tetragonal-ZrO2 + SiO2 [6]. Reidite and tertragonal-ZrO2 leave identifying relicts in the rocks, markers of the high pressures and/or temperatures these rocks underwent. Ries Crater is a 26-km-diameter peak ring crater in southern Germany that formed approximately 15 Ma [7–9]. Ries is the type locality of the polymict impact breccia known as suevite. Here, we report a microanalytical study of suevite from the Ries impact structure. These analyses are used to inform our understanding of the pressure and temperature conditions involved in creating a polymict impact breccia such as suevite in a peak ring crater. Sample Description: The sample, denoted 16RS08, originates from Otting Quarry, at 48.8777° N, 10.7921° E, approximately 17 km from the center of the Ries Crater in Germany (approximately 4 km outside the crater rim). The material recorded in sample 16RS08 is therefore considered an outer suevite. The outer suevite is a discontinuous layer of polymict impact breccia that occurs outside the central ring of Ries, up to 22 km from the center of the crater [9]. Lithic clasts in the outer suevite consist primarily of crystalline basement rocks (gneiss, granite, amphibolite), with less than 5% of lithic clasts being overlying sedimentary rocks (limestone, sandstone, shale) [9]. The thin section studied contains variably shocked lithic and mineral clasts, impact glass, and interstitial minerals that make up the matrix of the breccia (Fig. 1) [9]. Methods: We used a Cameca SX100 electron probe microanalyzer (EPMA) located in the Kuiper Materials Imaging and Characterization Facility (KMICF) at the University of Arizona to obtain 15 elemental X-ray maps of 16RS08. We next used the JEOL 7900F SEM at the Astromaterials Research & Exploration Science (ARES) at NASA Johnson Space Center (JSC) to obtain electron backscatter diffraction (EBSD) maps and energy dispersive X-ray spectroscopy (EDS) maps of select portions of the section. The EBSD data were collected under beam conditions of 20 kV, and ~9 μA, with step sizes varying from 0.05 to 2 μm. Following EBSD data collection, we processed the data using AZtecCrystal and MTEX, a free MATLAB toolbox. Results: We used the elemental X-ray maps to identify the areas of interest in the section, particularly phosphates and Zr-bearing grains. These areas of interest were then targeted for follow up EBSD and EDS analyses. We have identified, through combined EBSD and EDS analysis, the presence of zircon, reidite, and monoclinic-ZrO2 (baddeleyite) in 16RS08. In 16RS08, we have found singular grains of zircon, zircon with a vermicular baddeleyite halo (Fig. 2a), and granular zircon with reidite (Fig. 2b). The different Zr-rich phases and their corresponding textures signifies that this sample underwent a broad spectrum of pressure and temperature conditions during the impact event. For example, zircons surrounded by a vermicular baddeleyite and SiO2 intergrowth (i.e., Fig. 2a) have been shown to preserve evidence of the extremely high temperatures of impact melt, upwards of 2370 °C [2, 6]. Similarly, reidite and granular zircon (i.e., Fig. 2b) have been shown to preserve evidence of high pressure, as the transition to reidite occurs >30 GPa [3, 6]. Future Work: Next, we will process the EBSD and EDS data for these Zr-rich grains, specifically looking for indicators of cubic- or tetragonal-ZrO2 in the baddeleyite remnants and of shock-precursors to the reidite. To further inform our work, we will also obtain BSE images of these grains using a Hitachi S-4800 SEM in KMICF at the University of Arizona, as well as geochemical spot analyses via EPMA. The data collected will be used to constrain the formation conditions of the Ries Crater outer suevite. Acknowledgments: We thank Ken Domanik and Jerry Chang for their support with data collection. This work was supported by a University of Arizona RII Core Facilities Pilot Program grant and start-up funds to JJB. TME thanks A. Cavosie and N. Timms for assistance during field sampling. We acknowledge support from NASA’s Planetary Science Research program for analysis performed at JSC. References: [1] Melosh H. J. (1989) Oxf. U. Press. [2] Timms et al. (2017) EPSL 477, 52–58. [3] Cavosie et al. (2016) Geology 44:9, 703–706. [4] White et al. (2020) Nature Astr. 4, 974–978. [5] Crow C. A. et al. (2017) GCA 202, 264–284. [6] Timms et al. (2017) Earth-Sci. Rev. 165, 185–202. [7] Schmieder M. et al. (2018) GCA 220, 146–157. [8] Schwarz W. H. et al. (2020) M&PS 55:2, 312–325. [9] Stöffler et al. (2013) M&PS 43:4, 515–589.

Zircon↗

The use of an ion-beam source to alter the surface morphology of biological implant materials

An electron bombardment, ion thruster was used as a neutralized-ion beam sputtering source to texture the surfaces of biological implant materials. Scanning electron microscopy was used to determine surface morphology changes of all materials after ion-texturing. Electron spectroscopy for chemical analysis was used to determine the effects of ion texturing on the surface chemical composition of some polymers. Liquid contact angle data were obtained for ion textured and untextured polymer samples. Results of tensile and fatigue tests of ion-textured metal alloys are presented. Preliminary data of tissue response to ion textured surfaces of some metals, polytetrafluoroethylene, alumina, and segmented polyurethane were obtained.

Weigand, A. J.↗

AlGaAs growth by OMCVD using an excimer laser

AlGaAs has been grown on GaAs by laser assisted OMCVD using an excimer laser, wavelength 193 nm, and a Cambridge OMCVD reactor. Films were grown at temperatures of 450 and 500 C with the laser beam parallel to the surface and impinging onto the surface at 15 deg from parallel. The samples were heated by RF coils while the laser beam was perpendicular to the gas flow. Typical gas flow parameters are 12 slm of H2, 15 sccm of Ga(CH3)3, 13 sccm of Al(CH3)3, and a pressure of 250 mbar. The initial energy density of the beam at the surface was 40 mJ/sq cm, the pulse rate was 20 pps, and the growth time was 7 min. The films were analyzed by Auger electron spectroscopy for the aluminum concentration and by TEM for the surface morphology.

Warner, Joseph D.↗

Electron Beam Irradiated Intercalated CNT Yarns For Aerospace Applications

Multi-walled CNT yarns have been experimentally and commercially created to yield lightweight, high conductivity fibers with good tensile properties for application as electrical wiring and multifunctional tendons. Multifunctional tendons are needed as the cable structures in tensegrity robots for use in planetary exploration. These lightweight robust tendons can provide mechanical strength for movement of the robot in addition to power distribution and data transmission. In aerospace vehicles, such as Orion, electrical wiring and harnessing mass can approach half of the avionics mass. Use of CNT yarns as electrical power and data cables could reduce mass of the wiring by thirty to seventy percent. These fibers have been intercalated with mixed halogens to increase their specific electrical conductivity to that near copper. This conductivity, combined with the superior strength and fatigue resistance makes it an attractive alternative to copper for wiring and multifunctional tendon applications. Electron beam irradiation has been shown to increase mechanical strength in pristine CNT fibers through increased cross-linking. Both pristine and intercalated CNT yarns have been irradiated using a 5-megavolt electron beam for various durations and the conductivities and tensile properties will be discussed. Structural information obtained using a field emission scanning electron microscope, energy dispersive X-ray spectroscopy (EDS), and Raman spectroscopy will correlate microstructural details with bulk properties.

electrical wiring↗

Auger Spectroscopy of Hydrogenated Diamond Surfaces

An energy shift and a change of the line shape of the carbon core-valence-valence Auger spectra are observed for diamond surfaces after their exposure to an electron beam, or annealing at temperatures higher then 950 C. The effect is studied for both natural diamond crystals and chemical-vapor-deposited diamond films. A theoretical model is proposed for Auger spectra of hydrogenated diamond surfaces. The observed changes of the carbon Auger line shape are shown to be related to the redistribution of the valence-band local density of states caused by the hydrogen desorption from the surface. One-electron calculation of Auger spectra of diamond surfaces with various hydrogen coverages are presented. They are based on self-consistent wave functions and matrix elements calculated in the framework of the local-density approximation and the self-consistent linear muffin-tin orbital method with static core-hole effects taken into account. The major features of experimental spectra are explained.

Krainsky, I. L.↗

Fe and O EELS Studies of Ion Irradiated Murchison CM2 Carbonaceous Chondrite Matrix

Introduction: The physical and chemical response of hydrated carbonaceous chondrite materials to space weathering processes is poorly understood. Improving this understanding is a key part of establishing how regoliths on primitive carbonaceous asteroids respond to space weathering processes, knowledge that supports future sample return missions (Hayabusa 2 and OSIRISREx) that are targeting objects of this type. We previously reported on He+ irradiation of Murchison matrix and showed that the irradiation resulted in amorphization of the matrix phyllosilicates, loss of OH, and surface vesiculation. Here, we report electron energy-loss spectroscopy (EELS) measurements of the irradiated material with emphasis on the Fe and O speciation. Sample and Methods: A polished thin section of the Murchison CM2 carbonaceous chondrite was irradiated with 4 kilovolts He(+) (normal incidence) to a total dose of 1 x 10(exp 18) He(+) per square centimeter. We extracted thin sections from both irradiated and unirradiated regions in matrix using focused ion beam (FIB) techniques with electron beam deposition for the protective carbon strap to minimize surface damage artifacts from the FIB milling. The FIB sections were analyzed using a JEOL 2500SE scanning and transmission electron microscope (STEM) equipped with a Gatan Tridiem imaging filter. EELS spectra were collected from 50 nanometer diameter regions with an energy resolution of 0.7 electronvolts FWHM at the zero loss. EELS spectra were collected at low electron doses to minimize possible artifacts from electron-beam irradiation damage. Results and Discussion: Fe L (sub 2,3) EELS spectra from matrix phyllosilicates in CM chondrites show mixed Fe(2+)/Fe(3+) oxidation states with Fe(3+)/Sigma Fe approximately 0.5. Fe L(sub 2,3) spectra from the irradiated/ amorphized matrix phyllosilicates show higher Fe(2+)/Fe(3+) ratios compared to spectra obtained from pristine material at depths beyond the implantation/amorphization layer. We also obtained O Ka spectra from phyllosilicates in both regions of the sample. The O Ka spectra show a pre-edge feature at approximately 530.5 electronvolts that is related to O 2p states hybridized with Fe 3d states. The intensity ratio of the O Ka pre-edge peak relative to the main part of the O Ka edge (that results from transitions of O 1s to 2p states) is lower in the irradiated layer compared to the pristine material and may reflect the loss of O (as OH) as was observed by IR spectroscopy. Conclusions: In addition to amorphization and OH loss, EELS spectra of He(+) irradiated matrix phyllosilicates in Murchison show that some of the Fe(3+) is reduced to Fe(2+). Spectral deconvolution is underway to extract quantitative ratios from the EELS spectra.

Keller, L. P.↗

Electron-impact excitation of UF6 at an electron energy of 20 eV in the energy-loss range of 0-10 eV

A technique combining electron impact excitation and optical absorption spectroscopy was applied to UF6. The crucial features of the experiment were that: (1) the electron optics was differentially pumped relative to the scattering chamber and (2) the target UF6 beam was condensed on a liquid nitrogen cold trap placed immediately above the scattering center. Energy loss spectra are presented at an incident electron energy of 20 eV and at scattering angles between 20 and 135 degrees. It is shown that no transitions are found below the first-detected feature at 3.0 eV and an optically forbidden excitation is found at 4.2 eV. A fairly strong optical absorption at 4.8 eV is observed to 'fill-in' at a scattering angle of 20 degrees but is practically absent at higher angles.

Chutjian, A.↗

Diagnostic for Plasma Enhanced Chemical Vapor Deposition and Etch Systems

In order to meet NASA's requirements for the rapid development and validation of future generation electronic devices as well as associated materials and processes, enabling technologies ion the processing of semiconductor materials arising from understanding etch chemistries are being developed through a research collaboration between Stanford University and NASA-Ames Research Center, Although a great deal of laboratory-scale research has been performed on many of materials processing plasmas, little is known about the gas-phase and surface chemical reactions that are critical in many etch and deposition processes, and how these reactions are influenced by the variation in operating conditions. In addition, many plasma-based processes suffer from stability and reliability problems leading to a compromise in performance and a potentially increased cost for the semiconductor manufacturing industry. Such a lack of understanding has hindered the development of process models that can aid in the scaling and improvement of plasma etch and deposition systems. The research described involves the study of plasmas used in semiconductor processes. An inductively coupled plasma (ICP) source in place of the standard upper electrode assembly of the Gaseous Electronics Conference (GEC) radio-frequency (RF) Reference Cell is used to investigate the discharge characteristics and chemistries. This ICP source generates plasmas with higher electron densities (approximately 10(exp 12)/cu cm) and lower operating pressures (approximately 7 mTorr) than obtainable with the original parallel-plate version of the GEC Cell. This expanded operating regime is more relevant to new generations of industrial plasma systems being used by the microelectronics industry. The motivation for this study is to develop an understanding of the physical phenomena involved in plasma processing and to measure much needed fundamental parameters, such as gas-phase and surface reaction rates. species concentration, temperature, ion energy distribution, and electron number density. A wide variety of diagnostic techniques are under development through this consortium grant to measure these parameters. including molecular beam mass spectrometry (MBMS). Fourier transform infrared (FTIR) spectroscopy, broadband ultraviolet (UV) absorption spectroscopy, a compensated Langmuir probe. Additional diagnostics. Such as microwave interferometry and microwave absorption for measurements of plasma density and radical concentrations are also planned.

Cappelli, Mark A.↗

An e.s.c.a. study of atomic oxygen interactions with phosphazene-coated polyimide films

Metallic as well as most nonmetallic materials experience oxidation and mass loss via surface erosion in low earth orbit as shown in previous Space Shuttle flights. This study is an evaluation of select polyphosphazene polymers and their resistance to atomic oxygen attack. Electron spectroscopy for chemical analysis examinations of the surfaces of polyphosphazene coatings were monitored for microstructural changes induced during exposures to atomic oxygen. Sample exposures in oxygen plasmas and O(3P) beam were compared as to their effect on surface compositional changes in the polyphosphazene coating. High resolution line scans revealed rearrangements in the polymer backbone and scissioning reactions involving fluorocarbon units of long chain fluoroalkoxy pendant groups. Atom percents and peak areas of all species provided a detailed profile of the microstructural changes induced in phosphazene polymers as a result of exposures to atomic oxygen.

Fewell, Larry L.↗

Eucrite Impact Melt NWA 5218 - Evidence for a Large Crater on Vesta

Northwest Africa (NWA) 5218 is a 76 g achondrite that is classified as a eucrite [1]. However, an initial classification [2] describes it as a "eucrite shock-melt breccia...(in which) large, partially melted cumulate basalt clasts are set in a shock melt flow...". We explore the petrology of this clast-bearing impact melt rock (Fig. 1), which could be a characteristic lithology at large impact craters on asteroid Vesta [3]. Methods: Optical microscopy, scanning electronmicroscopy, and Raman spectroscopy were used on a thin section (Fig. 1) for petrographic characterization. The impact melt composition was determined by 20 m diameter defocused-beam analyses with a Cameca SX-100 electron microprobe. The data from 97 spots were corrected for mineral density effects [4]. Constituent mineral phases were analyzed with a focusedbeam. Bidirectonal visible and near-infrared (VNIR) and biconical FT-IR reflectance spectra were measured on the surface of a sample slab on its central melt area and on an eucrite clast, and from 125-500 m and <125 m powders of melt. Results: General petrography: The sample specimen is a coherent, medium dark-grey (N4), melt rock. The thin section captures a central, subophitic-textured melt that contains ~1 cm to tens of m-size subangular to rounded, variably-shocked eucrite clasts. Clasts >100 m are coarse-grained with equigranular ~1 mm size plagioclase, quartz, and clinopyroxene (Fig. 1). Single crystals of chromite, ilmenite, zircon, Ca-Mg phosphate, Fe-metal, and troilite are embedded in the melt. Polymineralic clasts are mostly compositionally similar to the above mentioned larger clasts but scarce granulitic fragments are observed as well.

Wittmann, Axel↗

Optimization of Picosecond Laser Parameters for Surface Treatment of Composites Using a Design of Experiments (DOE) Approach

Based on guidelines from the Federal Aviation Administration, research supported by the NASA Advanced Composites Project is investigating methods to improve process control for surface preparation and pre-bond surface characterization on aerospace composite structures. The overall goal is to identify high fidelity, rapid, and reproducible surface treatments and surface characterization methods to reduce the uncertainty associated with the bonding process. The desired outcome is a more reliable bonded airframe structure, and to reduce time to achieve certification. In this work, a design of experiments (DoE) approach was conducted to determine optimum laser ablation conditions using a pulsed laser source with a nominal pulse width of 10 picoseconds. The laser power, frequency, scan speed, and number of passes (1 or 2) were varied within the laser system operating boundaries. Aerospace structural carbon fiber reinforced composites (Torayca® 3900-2/T800H) were laser treated, then characterized for contamination, and finally bonded for mechanical testing. Pre-bond characterization included water contact angle (WCA) using a handheld device, ablation depth measurement using scanning electron microscopy (SEM), and silicone contamination measurement using laser induced breakdown spectroscopy (LIBS). In order to accommodate the large number of specimens in the DoE, a rapid-screening, double cantilever beam (DCB) test specimen configuration was devised based on modifications to ASTM D5528. Specimens were tested to assess the failure modes observed under the various laser surface treatment parameters. The models obtained from this DoE indicated that results were most sensitive to variation in the average laser power. Excellent bond performance was observed with nearly 100% cohesive failure for a wide range of laser parameters. Below about 200 mW, adhesive failure was observed because contamination was left on the surface. For laser powers greater than about 600 mW, large amounts of fiber were exposed, and the failure mode was predominately fiber tear.

Palmieri, Frank L.↗

Electron Beam Damage in Apatite: Limitations for SKα Measurements of S6+/∑S

In magmatic systems, the availabil- ity of excess oxygen that can react with multivalent elements such as Fe and S to change their charge (oxi- dation of Fe2+ to Fe3+ or reduction of S6+ to S2-) is characterized by a parameter called the oxygen fugacity (ƒO2). The ƒO2 controls the availability of these ions and consequently the minerals—and the chemistry of those minerals—that crystallize from a melt. Mineral mode and chemistry control how magmas evolve, and given that ƒO2 varies by many orders of magnitude on different planets [2], understanding the ƒO2 of a mag- ma is critical to relating observations about a magma to the body on which it forms. The mineral apatite was long thought to only incor- porate S6+ in a coupled substitution for P5+, but recently natural apatites with S2- were identified in lunar mare basalts that crystallized at low ƒO2 [3]. This suggests that apatite can be used as a monitor of ƒO2 assuming that one can 1) measure S6+/∑S (S6+ over total sulfur), and 2) determine some partitioning relationship be- tween apatite and melt for S6+ and S2-. The most common method for measuring S6+/∑S is X-ray Absorption Near-Edge Spectroscopy (XANES), but given the limited access to synchrotron facilities, it is wise to explore the potential of other methods for measuring S6+/∑S. One such possible method relies upon the shift in energy of the sulfur K-α peak on the electron microprobe. However, apatite is subject to well-documented beam damage [4, 5], so it is neces- sary to evaluate under what conditions can reliable S6+ ethod.

de Chizelle, J. Kuhn↗