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At least 1,189 records · Page 66

Evaluation of certain material films flown on the Space Shuttle Mission 46, EOIM-3 experiment

Nine film samples were carried aboard the STS-46 Atlantis shuttle to complement the 'Evaluation of Oxygen Interaction with Materials (EOIM-III)' experiment to evaluate the effects of atomic oxygen on materials and to monitor the gaseous environment in the shuttle bay. The morphological changes of the samples produced by the atomic oxygen fluence of 2.07E-20 atoms/sq cm have been reported. The changes have been verified using X-ray Photoelectron Spectrometer (XPS) also known as Electron Spectroscopy for Chemical Analysis (ESCA), gravimetric measurements, microscopic observations and thermo-optical measurements. The samples including Kapton, Tefzel, Aclar, Polyacrylonitrile film, and Llumalloy films have been characterized by their oxygen reaction efficiency on the basis of their erosion losses and the fluence. Those efficiencies have been compared with results from other similar experiments, when available. The efficiencies of the samples are all in the range of E-24 gm/atom.

Scialdone, John↗

Study of Neutron-Induced Stable and Radioactive Nuclides in a Post Detonation Urban Environment

In the event of a nuclear detonation in an urban environment, response time for triage by first responders, and forensic sample collection are of the utmost importance. When it comes to response planning, decision makers within the government need to have the most up-to-date information regarding several quantities of interest so that the maximum amount of lives can be saved. Quantities of interest in a post-detonation scenario include the spatial distribution of neutron-induced stable and radioactive isotopes in the environment, fallout patterns, blast and re damage zones [1]. The UMPRINDER toolkit is developed to calculate the prompt neutron-induced stable and radioactive isotopes in the surrounding environment in a nuclear forensics post-detonation scenario. The distribution of these isotopes in the environment can be used to provide guidance in determining best routes for first responders in order to minimize dose, debris sample collection routes for subsequent radiochemical analysis, and provide initial radionuclide inventories to fallout codes in order to improve fallout zone fidelity. Other methods have approached isotope transmutation on unstructured mesh for the fusion community concerning shutdown dose rates associated with fusion reactors. UMPRINDER is the first method to be focused on calculating some of the quantities of interest for the nuclear forensics and weapon effects communities.

61 RADIATION PROTECTION AND DOSIMETRY↗

The effect of cerium, neodymium, and ytterbium doping on UO 2 dissolution

Here, the dissolution rate of spent nuclear fuel has been studied heavily to understand the impacts of a failed waste package scenario on potential radionuclide release from a geologic repository. Multiple countries have evaluated these scenarios in oxidizing and reducing environments respective to their relevant repository conditions. The repository environment (e.g., water chemistry, temperature, oxygen content) and the fuel itself (e.g., chemical content of the fuel) both heavily impact the dissolution rate of the spent fuel. This work examined the impact that rare earth element dopants (Ce, Nd, Yb) have on the fuel dissolution under repository relevant conditions with decreasing oxidizing conditions using a single pass flowthrough system. UO 2 samples were doped with Ce, Nd, or Yb with concentrations between 1 and 5 at%. The addition of dopants to the samples reduced the dissolution rates on most samples relative to pure UO 2 samples. Scoping experiments that occurred in a less oxidizing environment showed a reduction in dissolution rate compared to fully oxidizing conditions. The results within highlight the importance of dopant behavior in used fuel dissolution modeling.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Distributed Spatiotemporal Motion Planning for Spacecraft Swarms in Cluttered Environments

This paper focuses on trajectory planning for spacecraft swarms in cluttered environments, like debris fields or the asteroid belt. Our objective is to reconfigure the spacecraft swarm to a desired formation in a distributed manner while minimizing fuel and avoiding collisions among themselves and with obstacles. In our prior work we proposed a novel distributed guidance algorithm for spacecraft swarms in static environments. In this paper, we present the Multi-Agent Moving-Obstacles Spherical Expansion and Sequential Convex Programming (MAMO SE-SCP) algorithm that extends our prior work to include spatiotemporal constraints such as time-varying, moving obstacles and desired time-varying terminal positions. In the MAMO SE-SCP algorithm, each agent uses a spherical-expansion-based sampling algorithm to cooperatively explore the time-varying environment, a distributed assignment algorithm to agree on the terminal position for each agent, and a sequential-convex-programming-based optimization step to compute the locally-optimal trajectories from the current location to the assigned time-varying terminal position while avoiding collision with other agents and moving obstacles. Simulation results demonstrate that the proposed distributed algorithm can be used by a spacecraft swarm to achieve a time-varying, desired formation around an object of interest in a dynamic environment with many moving and tumbling obstacles.

Bandyopadhyay, Saptarshi↗

Technology for return of planetary samples

The problem of returning a Mars sample to Earth was considered. The model ecosystem concept was advanced as the most reliable, sensitive method for assessing the biohazard from the Mars sample before it is permitted on Earth. Two approaches to ecosystem development were studied. In the first approach, the Mars sample would be introduced into the ecosystem and exposed to conditions which are as similar to the Martian environment as the constitutent terrestrial organisms can tolerate. In the second approach, the Mars sample would be tested to determine its effects on important terrestrial cellular functions. In addition, efforts were directed toward establishing design considerations for a Mars Planetary Receiving Laboratory. The problems encountered with the Lunar Receiving Laboratory were evaluated in this context. A questionnaire was developed to obtain information regarding important experiments to be conducted in the Planetary Receiving Laboratory.

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Part Marking and Identification Materials on MISSE

Many different spacecraft materials were flown as part of the Materials on International Space Station Experiment (MISSE), including several materials used in part marking and identification. The experiment contained Data Matrix symbols applied using laser bonding, vacuum arc vapor deposition, gas assisted laser etch, chemical etch, mechanical dot peening, laser shot peening, and laser induced surface improvement. The effects of ultraviolet radiation on nickel acetate seal versus hot water seal on sulfuric acid anodized aluminum are discussed. These samples were exposed on the International Space Station to the low Earth orbital environment of atomic oxygen, ultraviolet radiation, thermal cycling, and hard vacuum, though atomic oxygen exposure was very limited for some samples. Results from the one-year exposure on MISSE-3 and MISSE-4 are compared to those from MISSE-1 and MISSE-2, which were exposed for four years. Part marking and identification materials on the current MISSE -6 experiment are also discussed.

Finckenor, Miria M.↗

Technical Note: Isotopic corrections for the radiocarbon composition of CO 2 in the soil gas environment must account for diffusion and diffusive mixing

Earth system scientists working with radiocarbon in organic samples use a stable carbon isotope ( δ 13 C ) correction to account for mass-dependent fractionation, but it has not been evaluated for the soil gas environment, wherein both diffusive gas transport and diffusive mixing are important. Using theory and an analytical soil gas transport model, we demonstrate that the conventional correction is inappropriate for interpreting the radioisotopic composition of CO 2 from biological production because it does not account for important gas transport mechanisms. Based on theory used to interpret δ 13 C of soil production from soil CO 2 , we propose a new solution for radiocarbon applications in the soil gas environment that fully accounts for both mass-dependent diffusion and mass-independent diffusive mixing.

54 ENVIRONMENTAL SCIENCES↗

First-results from the Perseverance SHERLOC Investigation: Aqueous Alteration Processes and Implications for Organic Geochemistry in Jezero Crater, Mars

The Perseverance rover landed in Jezero crater, a site selected to fulfill the Mars-2020 mission goals of characterizing the geology of habitable environments and searching for signs of life while collecting samples for return to Earth [1]. Jezero hosted an open-basin lake during the late Noachian/early Hesperian (~3.7 Ga) [1-2], has units associated with the largest carbonate deposit identified on Mars [3-4], and has a well-preserved delta with clay and carbonate-bearing sediments, well-suited to preservation of organics [1,3-4]. Investigating the nature of organics and aqueous environments within their geologic con-text allows us to understand important aqueous processes and determine habitability within Jezero crater. Previous in situ landed measurements of organics could not resolve their spatial and mineralogical con-text [5-6]. Although Martian meteorites lack geological context, the spatial distribution of organic compounds in Martian meteorites have allowed recognition of an association between aqueous processes and organics [7-8]. Here, we show for the first time in-situ associations between carbonate-forming ultramafic alteration process, later stage aqueous sulfate and perchlorate formation, and organics on the Martian surface. Methodology and geological context: We use the Perseverance rover’s SHERLOC instrument (Scanning Habitable Environments with Raman and Lumines-ence of Organics and Chemicals), a deep-ultraviolet fluorescence and Raman scattering spectrometer capable of mapping the organic and mineral composition with a spatial resolution of 100 μm resolution to report the presence of organics and aqueously formed minerals at Jezero crater [9]. These spectral detections were compared with co-located images obtained with the autofocus context imager (ACI) and the WATSON camera for textural analysis [9]. As of writing, the Per-severance rover has abraded five targets that were measured with the SHERLOC instrument. The five targets are located in two different orbitally-identified geological units within the floor of Jezero crater; the Crater Floor Fractured Rough unit (CF-Fr) and the Séítah region within the Crater Floor Fractured 1 unit (CF-F1) [10]. In orbital infrared spectroscopic data, the CF-Fr unit is associated with pyroxene spectral signatures and minor alteration, while the Séítah region is associated with olivine and minor Mg-rich carbonates and clays [3-4,10]. Carbonation of ultramafic protolith recorded within Jezero crater: All scans of abraded targets within the Séítah region reveal strong peaks at 1080–1090 cm−1 consistent with carbonate and peak singlets or doublets at 820–840 cm−1 attributed to olivine (Fig. 1), consistent with orbital infrared observations. Our detailed micron-scale petrographic and spectroscopic evidence shows that these carbonates formed through carbonation of an ultramafic protolith. The supporting observations include: (1) Carbonate cation compositions match those of olivine, suggesting mixed Fe- and Mg-olivine gave rise to mixed Fe- and Mg-carbonates, similar to observations of ultramafic systems on Earth and within Martian meteorites [3-4,7-8]. (2) The ob-served carbonates co-occur with hydrated materials, gypsum, and potentially aqueously-formed phases, amorphous silicates and phosphate. (3) The spectral and textural variation of olivine and carbonate dominated zones and olivine-carbonate mixtures within both primary grains and interstitial zones are expected for carbonated ultramafic protoliths. (4) These mineral associations and textures closely resemble those observed within the ALH84001 and Nakhlite meteorites attributed to olivine carbonation on Mars [6-7]. Taken together, micron-scale SHERLOC documentation of these phenomena bridge previous orbital and meteorite observations and demonstrate in-situ regionally extensive (~106 km2) ultramafic alteration resulting in geo-logical deposition of carbonates. Furthermore, we observe that olivine carbonation was involved in preserving and possibly synthesizing organics, which makes this environment potentially habitable, as previously suggested in [1,3-4] (Fig. 1). Late-stage aqueous perchlorate and sulfate in Jezero crater: An abrasion target within the CF-Fr unit contains combinations of high intensity 950-955 cm−1 peaks and minor 1090-1095 cm−1 and 1150-1155 cm−1 peaks that are spectral fits to anhydrous perchlorate (Fig. 1). Some spectra show a combination of 950-955 cm−1 peaks with equally strong 1010-1020 cm−1 peaks, low intensity broad features at 1120 cm−1, and occasional broad 3450 cm−1 hydration (-OH) features, indicating a mixture of Ca-sulfate and perchlorate that is minimally hydrated (Fig. 1). The detections of per-chlorates within Jezero crater differ from previous measurements (e.g. Phoenix lander, Curiosity rover, Tissint meteorite [7,11]) because they are observed to be intimately related to aqueous processes including sulfate formation, they present as a secondary white void-fill occurring within the interior of the rock, and they are found to likely be Na-perchlorate. implications for their formation: Three different types of organics embedded within three different lithologies were observed within the abraded targets. Organics associated with low intensity ~340 nm fluorescence were widespread within targets with no apparent association to particular minerals (Fig. 1). Organics associated with ~305 nm and ~275 nm fluorescence correlated with sulfates within the Bellegarde target in the CF-Fr unit, while organics associated with high intensity ~340 nm fluorescence correlated with carbonate, phosphate, and amorphous silicate mixtures within the Garde target in the Séítah region (Fig. 1). Although assignment of fluorescence signatures to specific organic compounds is not conclusive, ~340 nm fluorescence is generally more consistent with 2-ring aromatic organics, ~275 nm fluorescence is more consistent with 1-ring aromatic organics, and ~305 nm fluorescence can be created by either 2- or 1-ring aromatics [12]. These observations indicate that the strongest fluorescence signatures interpreted as organics were found in materials associated with aqueous processes, i.e. sulfate- and carbonate-bearing materials, suggesting both brines and ultramafic carbonation aqueous environments were capable of preserving organics on ancient Mars. In Martian meteorites, simple aromatic organics proposed to have been synthesized through aqueous processes can be found within minerals associated with olivine carbonation and in spatial association with perchlorate and sulfate materials [7-8], similar to SHERLOC observations. Hence, we advance an abiotic aqueous synthesis origin for the organics although we cannot rule out the presence of organics from meteoritic in-fall or putative organic biosignatures. Detailed analyses will be required upon return of these materials to Earth.

E L Scheller↗

Beyond the tip of the iceberg; a new view of the diversity of sulfite- and sulfate-reducing microorganisms

Sulfite-reducing and sulfate-reducing microorganisms (SRM) play important roles in anoxic environments, linking the sulfur and carbon cycles. With climate warming, the distribution of anoxic habitats conductive to dissimilatory SRM is expanding. Consequently, we hypothesize that novel SRM are likely to emerge from the rare biosphere triggered by environmental changes. Using the dsrB gene as a molecular marker of sulfite-reducers and sulfate-reducers, we analyzed the diversity, community composition, and abundance of SRM in 200 samples representing 14 different ecosystems, including marine and freshwater environments, oil reservoirs, and engineered infrastructure. Up to 167,397 species-level OTUs affiliated with 47 different families were identified. Up to 96% of these can be considered as “rare biosphere SRM”. One third of the dsrB genes identified belonged to uncharacterized lineages. The dsrB sequences exhibited a strong pattern of selection in different ecosystems. These results expand our knowledge of the biodiversity and distribution of SRM, with implications for carbon and sulfur cycling in anoxic ecosystems.

59 BASIC BIOLOGICAL SCIENCES↗

Manned NEO Mission EVA Challenges

The President has proposed to land astronauts on an asteroid by 2025. However, Manned NEO (Near Earth Objects) Missions will present a host of new and exciting problems that will need to be better defined and solved before such a mission is launched. Here I will focus on the challenges for conducting asteroidal EVAs. Specfically, crew locomotion, sampling, drilling, documentation, and instrument deployment issues arising from the micro gravity environments associated with NEOs. Therefore, novel methods and techniques will need to be developed and tested in order to achieve specific mission science objectives. Walking or driving on the surface will not be a realistic option due to the small sizes (10 s to 100 s of meters in diameter) and hence extremely low gravity of the present day known candidate NEOs. EVAs will have to be carried out with crew members either using a self propelled device (akin to the MMU and SAFER units used on Shuttle/ISS) and or tethers. When using tethers a grid system could be deployed which is anchored to the asteroid. These anchor points could be inserted by firing penetrators into the surface from the spacecraft while it is still at a safe standoff distance. These penetrators would pull double duty by being laden with scientific instrumentation to probe the subsurface. Dust and debris generated by sample collection and locomotion in a microgravity environment could also pose some problems that will require forethought.

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Internal friction in rocks and its relationship to volatiles on the moon

The physical properties of lunar rocks were measured using the vibrating bar technique in order to provide data for interpretation of geophysical results such as those from seismic measurements. The effect of volatiles on the mechanical Q in lunar rocks was studied in addition to the effect of exposing a sample to controlled amounts of those gases most likely to be present in the lunar environment or likely to have been outgassed from the lunar interior. The moderate temperatures to which the sample was exposed during the thermal treatment and the small drop in resonant frequency during the course of the outgassing suggests that there was little change in microfracture density. The frequency, composition and texture dependence of the damping were investigated, to study the loss mechanism.

Tittmann, B. R.↗

Long-term measurements of ice nucleating particles at Atmospheric Radiation Measurement (ARM) sites worldwide

Ice nucleating particles (INPs) play a critical role in cloud microphysics and precipitation formation, yet long-term, spatially extensive observational datasets remain limited. Here, we present one of the most comprehensive publicly available datasets of immersion-mode INP concentrations using a single analytical method, generated through the U.S. Department of Energy's (DOE) Atmospheric Radiation Measurement (ARM) user facility. INP filter samples have been collected across a broad range of environments – including agricultural plains, Arctic coastlines, high-elevation mountain sites, marine regions, and urban areas – via fixed observatories, mobile facility deployments, and vertically-resolved tethered balloon system operations. We describe the standardized processing and quality assurance pipeline, from filter collection and processing using the Ice Nucleation Spectrometer to final data products archived on the ARM Data Discovery portal. The dataset includes both total INP concentrations and selectively treated samples, allowing for classification of biological, organic, and inorganic INP types. It features a continuous 5-year record of INP measurements from a central U.S. site, with data collection still ongoing. Seasonal and site-specific differences in INP concentrations are illustrated through intercomparisons at −10 and −20 °C, revealing distinct regional sources and atmospheric drivers. We also outline mechanisms for researchers to access existing data, request additional sample analyses, and propose future field campaigns involving ARM INP measurements. This dataset supports a wide range of scientific applications, from observational and mechanistic studies to model development, and provides critical constraints on aerosol-cloud interactions across diverse atmospheric regimes (Creamean et al., 2024, 2020b; https://doi.org/10.5439/1770816).

Creamean, Jessie M. [Colorado State Univ., Fort Co↗

Carbon and Oxygen Isotope Measurements of Ordinary Chondrite (OC) Meteorites from Antarctica Indicate Distinct Carbonate Species Using a Stepped Acid Extraction Procedure

The purpose of this study is to characterize the stable isotope values of terrestrial, secondary carbonate minerals from five Ordinary Chondrite (OC) meteorites collected in Antarctica. These samples were identified and requested from NASA based upon their size, alteration history, and collection proximity to known Martian meteorites. They are also assumed to be carbonate-free before falling to Earth. This research addresses two questions involving Mars carbonates: 1) characterize terrestrial, secondary carbonate isotope values to apply to Martian meteorites for isolating in-situ carbonates, and 2) increase understanding of carbonates formed in cold and arid environments with Antarctica as an analog for Mars. Two samples from each meteorite, each approximately 0.5 grams, were crushed and dissolved in pure phosphoric acid for 3 sequential reactions: a) R times 0 for 1 hour at 30 degrees Centigrade (fine calcite extraction), b) R times 1 for 18 hours at 30 degrees Centigrade (course calcite extraction), and c) R times 2 for 3 hours at 150 degrees Centigrade (siderite and/or magnesite extraction). CO (sub 2) was distilled by freezing with liquid nitrogen from each sample tube, then separated from organics and sulfides with a TRACE GC using a Restek HayeSep Q 80/100 6 foot 2 millimeter stainless column, and then analyzed on a Thermo MAT 253 Isotope Ratio Mass Spectrometer (IRMS) in Dual Inlet mode. This system was built at NASA/JSC over the past 3 years and proof-tested with known carbonate standards to develop procedures, assess yield, and quantify expected error bands. Two distinct species of carbonates are found: 1) calcite, and 2) non-calcite carbonate (future testing will attempt to differentiate siderite from magnesite). Preliminary results indicate the terrestrial carbonates are formed at approximately sigma (sup 13) C equal to plus 5 per mille, which is consistent with atmospheric CO (sub 2) sigma (sup 13) C equal to minus 7 per mille and fractionation of plus12 per mille based upon polar temperature of -20 degrees Centigrade. The oxygen values fractionate sigma (sup 18) O equal to minus 10-20 per mille lighter between the R times 0 and R times 1 reactions at 30 degrees Centigrade. The carbonate oxygen isotope measurements are consistently heavier than expected with meteoric water and temperatures from Antarctica, perhaps due to secondary carbonate formation during curation in Houston, TX.

Evans, Michael E.↗

Exposure of LDEF materials to atomic oxygen: Results of EOIM 3

The third Effects of Oxygen Atom Interaction with Materials (EOIM 3) experiment flew on STS-46 from July 31 to August 8, 1992. The EOIM-3 sample tray was exposed to the low-earth orbit space environment for 58.55 hours at an altitude of 124 nautical miles resulting in a calculated total atomic oxygen (AO) fluence of 1.99 x 10(exp 20) atoms/sq cm. Five samples previously flown on the Long Duration Exposure Facility (LDEF) Experiment M0003 were included on the Aerospace EOIM 3 experimental tray: (1) Chemglaze A276 white thermal control paint from the LDEF trailing edge (TE); (2) S13GLO white thermal control paint from the LDEF TE; (3) S13GLO from the LDEF leading edge (LE) with a visible contamination layer from the LDEF mission; (4) Z306 black thermal control paint from the LDEF TE with a contamination layer from the LDEF mission; and (5) anodized aluminum from the LDEF TE with a contamination layer from the LDEF mission. The purpose of this experiment was twofold: (l) investigate the response of trailing edge LDEF materials to atomic oxygen exposure, thereby simulating LDEF leading edge phenomena; (2) investigate the response of contaminated LDEF samples to atomic oxygen in attempts to understand LDEF contamination-atomic oxygen interactions. This paper describes the response of these materials to atomic oxygen exposure, and compares the results of the EOIM 3 experiment to the LDEF mission and to ground-based atomic oxygen exposure studies.

Jaggers, C. H.↗

Effect of pH on hydrogen pick-up and corrosion in zircaloy-4

Thermal Desorption Spectroscopy (TDS) has been used to investigate the hydrogen pick-up behaviour in different samples of Zircaloy-4. This includes as-received, cold rolled, hydrogen charged, and autoclave-oxidised in pure water and at an elevated pH (with 50% deuterated water) compared to commercial reactors. A characteristic desorption peak for hydrogen has been found at about 650 Celsius degrees, which is theorised to come from hydrides. Cold rolled samples show the same general shape spectrum as the as-received samples, with more hydrogen detected per unit volume of sample. This suggests more hydrogen is in trapping sites or outward diffusion paths are facilitated by dislocations, since no more hydrogen has been added. The peak broadens towards higher temperature, which indicates that additional dislocations could provide trapping sites with a slightly higher energy than the average in the as-received samples. The hydrogen charged samples form a hydride rim, which contains much more hydrogen than the as-received samples. The peak broadens but on average does not shift. The surface oxide, when present, acts as a barrier to the desorption of hydrogen, until the temperature rises enough for the oxygen to migrate into the bulk. The oxide itself only contains a small amount of hydrogen, as is evidenced when the oxide layer is removed, whereupon the desorption peak returns to the characteristic shape seen in as-received samples. Samples oxidised in pure water exhibit a slightly higher oxidation rate, and pass through kinetic transition much earlier than samples exposed to an elevated pH. Before transition pH has little effect on the hydrogen pick-up. After transition the hydrogen pick-up is much higher in pure water, which implies that the H{sup +} concentration in the environment affects hydrogen pickup at this stage. The elevated pH samples showed peaks for D-H and D{sub 2}, which follow the H{sub 2} peaks. The hydrogen content in these samples increases at around 70% of the time to the first transition. This may correlate with development of through-thickness percolation paths, which could lead to the pH inside cracks being modified to a lower value, increasing the availability of H{sup +} ions. (authors)

36 MATERIALS SCIENCE↗

Thermal shock resistance of lightweight cements developed for geothermal conditions

Cements are a critical component in well construction, as they act to prevent well fluid and gas escape, prevent corrosion of the casing, and strengthen the wellbore to prevent deformation. Under the high temperature/pressure conditions common in geothermal systems, the injection of cold water for energy production is expected to induce cyclic damage to the borehole cement through the rapid temperature fluctuations. These “thermal shocks” are expected to cause casing shrinkage, annulus formation, and cement tensile stresses. To understand the effect of cold water injection on the wellbore environment, a set of rock-cement-steel samples were created to simulate the structure of a geothermal well. Lightweight thermally-insulating cement blends were tested under thermal shock conditions in this study. In each test, the samples were pressurized to an effective pressure of ~3.5 MPa and placed at high temperatures. Thermal shocks were performed by injecting cold water (~10-15 °C) through the samples at a constant rate while keeping the samples at high temperatures until the sample temperature stopped decreasing and deformation ceased. Eight thermal shock tests were conducted with each sample – two at 100 °C and six at 200 °C. Post-tests analysis was then conducted by cutting open each sample to examine the damage in each component of the simulated wellbore. Experimental results suggest that all samples experienced similar degrees of axial and lateral contraction during cold water injection, but for the most part this contraction is recoverable when injection halts. Post-test analysis revealed that fly ash cenosphere pre-treatment had the best effect on improving thermal shock resistance in the cement blends. Thermomechanical modeling of likely stress paths experienced by the cements during heating/cooling cycles shows that elasto-plastic cement constitutive behavior results in most plastic strain occurring during the initial heating steps, with mostly elastic strain occurring during the thermal shock cycles. In conclusion, this agrees with experimental evidence, suggesting that cement damage from shocking occurs via other mechanisms such as chemical alteration, corrosion, and fatigue.

36 MATERIALS SCIENCE↗

Effect of amine type on acidic toxic gas adsorption at ambient conditions on modified CuBTC

We report two amine-modified copper-based Metal Organic Frameworks (MOF (CuBTC)) of different surface chemical and textural features were synthesized and used as adsorbents of acidic toxic gases (NO 2 and H 2 S) in both moist (71% relative humidity (R.H.)) and dry conditions. The initial and exhausted samples were characterized by nitrogen adsorption, powder X-ray diffraction, scanning electron microscopy, thermal gravimetric analysis and Fourier transform infrared spectroscopy. The addition of melamine prevented full growth of CuBTC crystals and resulted in amorphous-like particles with sizes less than 200 nm. The material was non-porous with a small surface area. When urea was used as an amine source, the resulting particles maintained the overall octahedral shape of the parent CuBTC MOF and the material was more porous than the parent MOF. While the urea-modified CuBTC sample performed well as an NO 2 adsorbent in the presence of moisture, the reactivity of the melamine-modified sample and its physical properties provided a favorable environment for the removal of H 2 S. The incorporation of amines into the MOF structure also resulted in surface defects /open copper sites that favored the removal of toxic gases in dry conditions. The reactivity of the adsorbents with toxic gases was demonstrated by the changes in the adsorbent colors, in texture, and in surface chemistry (organic salts, complexes, sulfides and nitrates were formed).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗