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Extraction Chromatographic Materials for Clean Hydrometallurgical Separation of Rare-Earth Elements Using Diglycolamide Extractants

The uncertain supply of the rare-earth elements (REE) from conventional sources such as bastnaesite and monazite demands the search for alternative sources. Unconventional sources such as phosphate rock and mine tailings have REE contents at the level of only hundreds to a thousand parts per million, which challenges the conventional REE separation methods such as solvent extraction (SX) and ion exchange (IX). Alternatively, the potential of extraction chromatography (EXC) has been explored, as it combines the selectivity of SX and the convenience of column techniques of IX. Herein, we report a novel EXC material incorporating N , N '-dimethyl- N , N '-dioctyl-3-oxa-diglycolamide (DMDODGA) into a porous solid support because DMDODGA exhibits higher extraction efficiency for REE in SX than does conventional N , N , N ', N '-tetraoctyl-3-oxa-diglycolamide (TODGA) and as also compared with similarly made conventional TODGA-based EXC material. The extraction of mixed REE by DMDODGA and TODGA resins was evaluated in H 2 SO 4 , HCl, and HNO 3 media as a function of acid concentration. The REE feed concentrations were adjusted to achieve stoichiometric REE concentration and excess REE concentration, conditions that reflect near or complete saturation of resin capacity. In general, extraction at the same acid concentration followed the order HNO 3 > HCl > H 2 SO 4 . The extraction strength of the DMDODGA resin is significantly higher than that of the TODGA resin in all three examined mineral acids, especially at lower H 2 SO 4 and HCl concentrations (0.01 and 0.1 M), making it a promising EXC material for hydrometallurgical extraction of REE.

Momen, Abdul↗

Missile impact craters (White Sands Missile Range, New Mexico) and applications to lunar research: Contributions to astrogeology

Craters in natural materials at White Sands Missile Range, N. Mex., were produced by the impact of high-velocity to hypervelocity missiles traveling along oblique trajectories with kinetic energies between 2.1 and 81 × 1014 ergs. The oblique impacts produce craters 2 to 10 m across with morphologies and ejecta that are bilaterally symmetrical with respect to the plane of the missile trajectory. Rims are high and the amount of ejecta large in down-trajectory and lateral directions, whereas rims are low to nonexistent and ejecta thin to absent up-trajectory. Symmetry development and modifications of the symmetry are a function of target material, local topography, and angle of impact. Seven mappable units can be recognized in and around the craters. Three of these are ejecta: thick ejecta near the crater, thin to discontinuous ejecta at greater distances, and scattered ejecta at the greatest distances to the limit of throwout. These ejecta units may be absent on the up-trajectory side; if present, they are rarely as thick or continuous as on other sides of the crater. Three units are target materials: undeformed target material exposed in local patches through thin to discontinuous ejecta and everywhere between the fragments of scattered ejecta, tilted and broken target material exposed in upper crater walls, and shattered and fractured target material exposed on the up-trajectory crater wall. The seventh unit is slope material composed of talus and fallback within the crater. Development, character, and exposure of these units varies chiefly with the target material. Ejecta from the craters is chiefly broken but relatively undeformed target material that may range in size from very fine grained debris to large blocks. Where the target is porous, significant amounts of the ejecta are composed of sheared and compressed fragments, some coated with dark layers of mixed projectile pieces, powder, and fused metal mixed with crushed target material. For layered targets, the original stratigraphic sequence is crudely preserved and in inverted order in thick ejecta. Secondary impact craters are produced by the impact of ejected fragments when the surrounding surface materials are sufficiently weak. A wide variety of secondary impact crater relations may result. Secondary craters nearest the primary crater have blocks in them that are larger than or the same size as the crater they produced. Farther from the primary crater, the fragments are generally smaller than the secondary crater and are ejected from it. Excavation of four craters revealed a mixed breccia beneath the crater floor composed of missile pieces, sheared and compressed target material, and crushed debris. Banded, disaggregated target material and nonmixed breccia surrounded the mixed breccia, and these breccias were surrounded by a zone of conjugate fractures. Beneath the ejecta on the lateral and down-trajectory crater flanks, the target materials were tilted upward and broken. Up-trajectory, open fractures and downward displacement occurred in two of the craters. No displacement was observed for the other two. Beneath the down-trajectory rims of craters with distinct layering, overturned synclines were observed. Missile breakup and behavior during cratering are a function of target and missile properties. Missile breakup depends on missile velocity and is most extensive at high velocities, where the missile is fragmented, powdered, and partly fused. Burial of missile or its fragmented, powdered, and fused remains is greatest for porous targets and least for dense cohesive targets. For very porous targets, camouflet structures containing the fragmented missile may form. Least squares fit to the data on craters in dry to moist targets indicate V(a) = 10^(-11.433)E(p)^(1.205) where V(a) is the volume of the apparent crater and E(p) is the kinetic energy of the missile. This equation is consistent with expectations of the equations relating apparent depth and radius to kinetic energy. Extrapolation of displaced masses and kinetic energies for laboratory impacts with sand and rock converge near 10^(15) to 10^(16) ergs, where the extrapolations are near the data on missile impact craters, corrected for impact angle. Displaced masses of craters produced by missile impacts and by chemical explosives with small scaled depths of burial are about the same when the kinetic energies of the missiles (corrected for angle of impact) are equal to the TNT equivalent energy of the explosive. The problem of equivalent scaled depth of burst for an impact crater is complicated and not entirely resolved, however. Both missile impact craters and chemical explosive craters in water-saturated targets are larger than their counterparts in dry to moist materials. Data collected during the study of missile impact craters have helped resolve a number of problems in lunar research: (1) the soillike nature of lunar surface materials was predicted, (2) sizes of craters produced by artificial impacts were correctly predicted, (3) certain features imaged by Surveyor were found to be analogous to features associated with missile impact craters, {4) missile impacts were used in support of the Apollo passive seismic experiment, (5) craters seen in Apollo orbital photographs were found to be similar to some missile impact craters, (6) missile impact craters supplied data on sample collection and crater phenomenology used in training astronauts, and (7) some returned lunar samples are similar to coated, sheared, and compressed fragments ejected from missile impact craters.

H. J. Moore↗

Permeability of Rigid Fibrous Refractory Insulations

Rigid fibrous refractory insulations (TPS tiles) are integral components of many spacecraft thermal protection systems. These materials are composed of refractory fibers With diameters on the order of 1 to 15 micrometers. They are lightweight and have an open, highly porous microstructure. Typical densities are less than 500 kilograms per cubic meters, and porosities generally exceed 0.8. Because of their open porosity, these materials are permeable to gas glow. There are numerous instances in which internal gas transport in a thermal protection system could be important; examples include the penetration of hot boundary-layer gases into the insulation, the flow of decomposition (pyrolysis) products from the interior, the use of convective flows to mitigate ice formation caused by cryopumping, and the design of refractory vents for pressure equilibration during atmospheric entry. Computational analysis of gas flow through porous media requires values of permeability which have not previously been available for the rigid fibrous insulations used in thermal protection systems. This paper will document measurements of permeability for a variety of insulations from NASA's LI, FRCI, and AETB families of lightweight ceramic ablators. The directional anisotropy of permeability and its dependence on gas pressure and material density will be presented. It will be shown that rarified-flow effects are significant in the flow through such materials. Connections will be drawn between the insulation microstructure and permeability. The paper will also include representative computations of flow through rigid fibrous insulations.

Marschall, J.↗

Carbon petrology in cometary dust

Chondritic porous (CP) interplanetary dust particles (IDP's) are collected in the Earth's stratosphere. There exists an extensive database on major and minor element chemistry, stable isotopes, noble gas abundances and mineralogy of many CP IDP's, as well as infrared and Raman spectroscopic properties. For details on the mineralogy, chemistry and physical properties of IDP's, I refer to the reviews by Mackinnon and Rietmeijer (1987), Bradley et al. (1988) and Sandford (1987). Texture, mineralogy (Mackinnon and Rietmeijer, 1987) and chemistry (Schramm et al., 1989; Flynn and Sutton, 1991) support the notion that CP IDP's are a unique group of ultrafine-grained extraterrestiral materials that are distinct from any known meteorite class. Their fluffy, or porous, morphology suggests that CP IDP's probably endured minimal alteration by protoplanetary processes since their formation. It is generally accepted that CP IDP's are solid debris from short-period comets. The evidence is mostly circumstantial but this notion gained significant support based on the comet Halley dust data (Brownlee, 1990). In this paper, I will accept that CP IDP's are indeed cometary dust. The C/Si ratio in CP IDP's is 3.3 times higher than in CI carbonaceous chondrites (Schramm et al. 1989). The intraparticle carbon distribution is heteorogeneous (Rietmeijer and McKay, 1986). Carbon occurs both in oxidized and reduced forms. Analytical electron microscope (AEM) and Raman spectroscopic analyses have shown the presence of several carbon forms in CP IDP's but the data are scattered in the literature. Carbons in cometary CP IDP's are among the most pristine Solar System carbons available for laboratory study. Similar to a recently developed petrological model for the diversity of layer silicates in CP IDP's (Zolensky, 1991) that is useful to constrain in situ aqueous alteration in comets (Rietmeijer and Mackinnon, 1987a), I here present the first effort to develop a petrological concept of carbons in CP IDP's. This concept is useful to constrain comet evolution. I also present the philosophical constraint facing Earth Scientists in studies of protoplanets that require a new approach to cometary dust studies.

Rietmeijer, Frans J. M.↗

Fast-Response-Time Shape-Memory-Effect Foam Actuators

Bulk shape memory alloys, such as Nitinol or CuAlZn, display strong recovery forces undergoing a phase transformation after being strained in their martensitic state. These recovery forces are used for actuation. As the phase transformation is thermally driven, the response time of the actuation can be slow, as the heat must be passively inserted or removed from the alloy. Shape memory alloy TiNi torque tubes have been investigated for at least 20 years and have demonstrated high actuation forces [3,000 in.-lb (approximately equal to 340 N-m) torques] and are very lightweight. However, they are not easy to attach to existing structures. Adhesives will fail in shear at low-torque loads and the TiNi is not weldable, so that mechanical crimp fits have been generally used. These are not reliable, especially in vibratory environments. The TiNi is also slow to heat up, as it can only be heated indirectly using heater and cooling must be done passively. This has restricted their use to on-off actuators where cycle times of approximately one minute is acceptable. Self-propagating high-temperature synthesis (SHS) has been used in the past to make porous TiNi metal foams. Shape Change Technologies has been able to train SHS derived TiNi to exhibit the shape memory effect. As it is an open-celled material, fast response times were observed when the material was heated using hot and cold fluids. A methodology was developed to make the open-celled porous TiNi foams as a tube with integrated hexagonal ends, which then becomes a torsional actuator with fast response times. Under processing developed independently, researchers were able to verify torques of 84 in.-lb (approximately equal to 9.5 Nm) using an actuator weighing 1.3 oz (approximately equal to 37 g) with very fast (less than 1/16th of a second) initial response times when hot and cold fluids were used to facilitate heat transfer. Integrated structural connections were added as part of the net shape process, eliminating the need for welding, adhesives, or mechanical crimping. Inexpensive net-shape processing was used, which reduces the cost of the actuator by over a factor of 10 over nonporous TiNi made by hot drawing of tube or electrical discharge machining. By forming the alloy as an open-celled foam, the surface area for heat transfer is dramatically increased, allowing for much faster response times. The technology also allows for netshape fabrication of the actuator, which allows for structural connections to be integrated into the actuator material, making these actuators significantly less expensive. Commercial applications include actuators for concepts such as the variable area chevron and nozzle in jet aircraft. Lightweight tube or rod components can be supplied to interested parties.

Jardine, Peter↗

The Deflagration-to-Detonation Transition in Two Dimensions

The Deflagration-to-Detonation Transition (DDT) in one-dimensional porous explosive, where combustion in an explosive transitions to detonation, can be described by the following model. This simplified model proceeds in five steps, as follows: 1) Ignition of the explosive, surface burning. 2) Convective burning, with the flame front penetrating through the porous network of the explosive. This proceeds until the pressure grows high enough to result in choked flow in the pores restricting the convective burn. 3) The choked flow results in the formation of a high-density compact of explosive. This compact is driven into undisturbed material by the pressure of the burning explosive. 4) The compression of the undisturbed porous explosive by the compact leads to the ignition of a compressive burn. This builds in pressure until a supported shock forms. 5) The shock builds in pressure until detonation occurs. See Figures 1 and 2 for an overview of the proceeding steps. It has been assumed in the past that the same mechanism which drives DDT in the one dimensional case will apply to both two and three dimensions. However, this has never been experimentally verified and it is possible that an entirely new mechanism drives DDT higher dimensions. In order to test this a series of two dimensional DDT tests were performed to help provide empirical evidence of the mechanism in higher dimensions.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Surface oxygen exchange kinetics of mixed conducting oxides: Dilatometric vs electrical conductivity relaxation study

The surface oxygen exchange kinetics of mixed ionic-electronic conducting (MIEC) oxides play a crucial role in a variety of applications, including solid oxide fuel/electrolysis cells (SOFCs/SOECs), permeation membranes and sensors. To date, a variety of methods, including isotope exchange, electrical conductivity, optical absorptivity and thermogravimetry relaxation, and impedance spectroscopy have been used to measure the oxygen exchange coefficient of MIEC oxides. Each of these methods have their advantages and limitations, depending on the physical and chemical properties of the investigated materials and their sample dimensions and densities. Here, we demonstrate the ability to precisely measure the surface oxygen exchange coefficient (k chem ) of MIEC model material Pr 0.1 Ce 0.9 O 2-δ (PCO) by use of dilatometric relaxation measurements, particularly of interest for materials that exhibit larger chemical expansion coefficients. This is achieved by use of porous bulk specimens to ensure that the contribution of oxygen exchange to the overall kinetics is dominant. We demonstrate that k chem values extracted from chemical expansion relaxation measurements on PCO are nearly identical to those derived from electrical conductivity relaxation measurements. As a result, this provides the opportunity to precisely investigate the oxygen exchange and chemical expansion kinetics of a wide range of materials used in high-temperature applications, particularly where more conventional methods are difficult or inappropriate to apply.

(Pr,Ce)O2-x↗

Large Primtive Asteroids: Thermal and Dynamical Context

Primitiveasteroids, most of which are located in the outer belt and Jupiter’s Trojan clouds, provide information related to the origin and evolution of the solar system and the conditions in which the solar nebula was formed. These asteroids are widely thought to be the origin of the least-altered car-bonaceous chondrite that allow us to put crucial con-straints on the current dynamical and thermal theories of the formation and evolution of the early solar sys-tem. The nature of surface composition of large and low-albedo asteroids, like (1) Ceres, (10) Hygiea and (52) Europa, is still under intense debate and different interpretations have beenput forth to explain the ab-sorption features in these objects (e.g.,[1, 2, 3,4,5,6]). Laboratory and spectroscopic experiments on me-teorites that represent all nine carbonaceous chondrite types also found no spectral matches for these large asteroids (e.g.,[7]). Previous studies of asteroid Ceres (the largest primitive asteroid in the solar system) have been conducted to constrain and estimate its surface composition (e.g., [2, 5]). Using linear mixing,[2]found hydroxide brucite, serpentines, and carbonates, to be consistent with Ceres’ ground-based spectra.[5]estimated the surface composition of Ceres and found evidence of widespread NH3-phyllosilicates across its surface using best-fit solutions to Dawn’s NIR spectra. The presence of NH3-phyllosilicates implies that mate-rial from the outer solar system was incorporated into large primitive asteroids, either during their formation at great heliocentric distance or by incorporation of material transported into the Main Belt region. Here we presentnew largeand primitive asteroidsthat share the same spectral similaritieswith the largest asteroid in the solar system, Ceres.We also present the context of these new observations in terms oftheirthermal and dynamicalevolution.Large Primitive Asteroids: Dynamical and Thermal Context:Orbital Distribution of LargePrimitiveAsteroids: Constraining the mineralogy and surface composition of large primitive asteroids will place crucial con-straints on existing dynamical and thermal theories of the formation of the early solar system. We identified several additional asteroids in the Europa-like group in addition to asteroids Europa, Euphrosyne, and Patien-tia, that wereidentified in [8]using NASA IRTFtele-scope (e.g.,Figure 1). These new asteroids along with the already-observed Ceres-and Europa-like group members are localized in the 2.8 < a < 3.4 AU region and characterized by larger sizes, showing an interest-ing orbital distribution (Figure 2). Ceres-likeand Eu-ropa-like groups, which include the largest asteroids in the solar system, show an interesting orbital distribu-tion. These groups are located in the 2.6 < a < 3.6 AU region that contains the snow-line. The snow-line’s location may have been driftedinwards due to the disk’s cooling and evolution[9,10]. Recent dynamical models[11,12]suggested that a substantial fraction of primitive asteroids originated between or beyond the giant planets (a > 5 AU), where water ice would have been stable, and then implanted in the outer Main Belt region because of the giant planets’ growth.Figure 1. Two asteroids, 94 Aurora and 423 Diotima, showing spectra similar to asteroids (1)Ceres and (52)Europa.Thermal modeling and evolution of primitive aster-oids:Primitive water-rich asteroids are thought to be originally composed of mixtures of anhydrous materi-als and water ice that waslater melted by heating sources such as the decay of 26Al, reacting with anhy-drous materials to form H2O/OH-rich minerals. Calcu-lations of the evolution of the temperature and struc-ture of icy planetesimals were performedusing a 1D finite differences thermal evolution model[13, 14] for 26Al-heated planetesimals. In particular, thermally activated compaction due to hot pressing of bodies with an initially unconsolidated porous structure is included. An ice-rich initial composition that leads to a material dominated by phyllosilicates upon aqueous alteration (with 25 vol% H2O and a rock fraction that contains 85 vol% phyllosilicates and 15 vol% olivine upon aque-ous alteration, similar to CIand CM chondrites) was assumed. Atypical initial porosity of 40%[15] is re-duced following the change of the strain rate that is calculated as Voigt approximation from the strain rates of components[16]. Material properties (thermal con-ductivity, density, heat capacity, etc.) correspond to the composition assumed and are adjusted with tempera-ture and porosity. Melting of the water ice as well as water-rock separation are included[14]. Both short-and long-lived radionuclides are consideredas heat sources. Figure 3 shows the maximum temperature calculated as a function of radius and accretion time. A variety of internal structures is obtained, ranging from primordial (no melting of water ice) over partially melted or partially differentiated (melting of water ice, hydration, formation of a rocky core and water ocean below an undifferentiated layer) to completely differ-entiated ones (rocky core, water mantle, Enceladus-like case). The heating and differentiation of planetesi-mals is determined by the availability of 26Al, i.e., by the accretion time t0 relative to the formation of the calcium-aluminum-rich inclusions (CAIs), such that maximum temperatures and structures vary stronglyfor t0< 6 Myr rel. to CAIs. However, for a later accre-tion only the size of the body determines its maximum tempera-ture and structure due to the nearly constant heating by long-lived radionuclides. Average densities of Ceres-and Europa-like group membersimply high-ly porous interiors and, consequently, relatively late accretion at t0> 3 Myr rel. to CAIs with a maximum temperature of < 600 K (Figure3)

D Takir↗

Unraveling the Ion Adsorption Kinetics in Microporous Carbon Electrodes: A Multiscale Quantum-Continuum Simulation and Experimental Approach

With the understanding that sorption in porous carbon electrodes is crucial to many environmental and energy technologies, such as capacitive deionization (CDI), supercapacitor energy storage, and activated carbon filters. In each of these examples, a practical model that can describe ion electrosorption kinetics is highly desirable for accelerating material design. Here, we proposed a multiscale model to study the ion electrosorption kinetics in porous carbon electrodes by combining quantum mechanical simulations with continuum approaches. Our model integrates the Butler-Volmer (BV) equation for sorption kinetics and a continuously stirred tank reactor (CSTR) formulation with atomistic calculations of ion hydration and ion-pore interactions based on density functional theory (DFT). We validated our model experimentally by using ion mixtures in a flow-through electrode CDI device and developed an in-line UV absorption system to provide unprecedented resolution of individual ions in the separation process. We showed that the multiscale model captures unexpected experimental phenomena that cannot be explained by the traditional ion electrosorption theory. The proposed multiscale framework provides a viable approach for modeling separation processes in systems where pore sizes and ion hydration effects strongly influence the sorption kinetics, which can be leveraged to explore possible strategies for improving carbon-based and, more broadly, pore-based technologies

36 MATERIALS SCIENCE↗

Accessibility and Mechanical Stability of Nanoporous Zinc Oxide and Aluminum Oxide Coatings Synthesized via Infiltration of Polymer Templates

The conformal nanoporous inorganic coatings with accessible pores that are stable under applied thermal and mechanical stresses represent an important class of materials used in the design of sensors, optical coatings, and biomedical systems. Here, we synthesize porous AlO x and ZnO coatings by the sequential infiltration synthesis (SIS) of two types of polymers that enable the design of porous conformal coatings—polymers of intrinsic microporosity (PIM) and block co-polymer (BCP) templates. Using quartz crystal microbalance (QCM), we show that alumina precursors infiltrate both polymer templates four times more efficiently than zinc oxide precursors. Using the quartz crystal microbalance (QCM) technique, we provide a comprehensive study on the room temperature accessibility to water and ethanol of pores in block copolymers (BCPs) and porous polymer templates using polystyrene-block-poly-4-vinyl pyridine (PS75-b-P4VP25) and polymers of intrinsic microporosity (PIM-1), polymer templates modified by swelling, and porous inorganic coatings such as AlO x and ZnO synthesized by SIS using such templates. Importantly, we demonstrate that no structural damage occurs in inorganic nanoporous AlO x and ZnO coatings synthesized via infiltration of the polymer templates during the water freezing/melting cycling tests, suggesting excellent mechanical stability of the coatings, even though the hardness of the inorganic nanoporous coating is affected by the polymer and precursor selections. We show that the hardness of the coatings is further improved by their annealing at 900 °C for 1 h, though for all the cases except ZnO obtained using the BCP template, this annealing has a negligible effect on the porosity of the material, as is confirmed by the consistency in the optical characteristics. These findings unravel new potential for the materials being used across various environment and temperature conditions.

36 MATERIALS SCIENCE↗

Digital light processing of porous LLZTO scaffolds for Li-garnet solid-state batteries

Li 7 La 3 Zr 2 O 12 (LLZO)-based solid-state electrolytes (SEs) are promising materials for next-generation solid-state batteries. In this work, digital light processing (DLP), an emerging additive manufacturing technology, is employed to produce porous Ta-doped LLZO (LLZTO) scaffolds. The self-standing scaffolds are 100 μm thick and have 40% porosity. The scaffolds demonstrate symmetric cell cycling stability exceeding 1,500 h at 0.1 mA/cm2 current density, with a capacity of 0.1 mAh/cm 2 (1 h for each half cycle). At higher current densities, reversible soft shorts frequently happen, while immediate hard shorts are prevented due to Li dendrite growth being hindered by the tortuous pore network. In addition to the cycling stability, the phase stability of LLZTO is investigated during the post-printing thermal process for printing resin removal. We discovered that the LLZTO partially decomposes into Li 2 Zr 2 O 7 and other impurity phases from 400°C to 800°C, but the pure LLZTO phase is restored upon the completion of resin removal beyond 800°C.

Li-metal anode↗

Scalable Graphene Oxide Hollow Fiber Membranes for Dye Desalination Enabled by Multi‐Purpose Polyamine Functionalization

2D nanosheets such as graphene oxide (GO) can be stacked to construct membranes with fine-tuned nanochannels to achieve molecular sieving ability. These membranes are often thin to achieve high water permeance, but their fabrication with consistent nanostructures on a large scale presents an enormous challenge. Herein, GO-based hollow fiber membranes (HFMs) are developed for dye desalination by synergistically combining chemical etching to form in-plane nanopores (10–30 nm) to increase water permeance and polyamine functionalization to improve underwater stability and enable facile large-scale production using existing membrane manufacturing processes. HFM modules with areas of 88 cm 2 and GO layer thicknesses of ≈500 nm are fabricated, and they exhibited a stable dye water permeance of 75 L m −2 h −1 bar −1 , rejection of >99.5% for Direct red and Congo red, and Na 2 SO 4 /dye separation factor of 300–500, superior to state-of-the-art commercial membranes. Furthermore, the versatility of this approach is also demonstrated using different short polyamines and porous substrates. This study reveals a scalable way of designing 2D materials into high-performance robust membranes for practical applications.

amine functionalization↗

Time-Resolved Neutron Imaging for Hydrogen Uptake in Subsurface Lithologies

Geologic hydrogen production and underground storage are increasingly important for meeting rising energy demands while providing clean-combustion advantages. However, hydrogen’s high diffusivity and propensity for leakage through porous media necessitate direct evaluation of its transport behavior in subsurface materials. Whereas X-ray microcomputed tomography (μCT) studies often employ contrast agents or surrogate gases, this study leverages neutron transmission radiography/CT to observe hydrogen migration in situ. This work represents the first demonstration of real-time neutron radiography of hydrogen migration in reservoir and caprock lithologies. Cylindrical cores of Indiana limestone, Amherst Gray sandstone, and Tumey shale were subjected to constant-pressure hydrogen charging and scanned in real time using high-resolution neutron radiography. Results indicate immediate hydrogen infiltration in sandstone and limestone, with homogeneous distribution detected throughout their pore structure. In contrast, hydrogen remained largely absent from fine-grained shale under the same pressure, except in an apparently localized fracture zone, where neutron signatures confirmed the presence of hydrogen. Subsequent neutron CT of the sandstone sample, using image subtraction against an uncharged reference, corroborated hydrogen distribution patterns. Even under lowpressure, single-phase conditions, distinct neutron imaging signatures of hydrogen were achieved. These preliminary findings underscore the potential of neutron imaging for advancing subsurface hydrogen migration research.

08 HYDROGEN↗

The nature and origins of decametre-scale porosity in Ordovician carbonate rocks, Halahatang oilfield, Tarim Basin, China

At >7 km depths in the Tarim Basin, hydrocarbon reservoirs in Ordovician rocks of the Yijianfang Formation contain large cavities ( c . 10 m or more), vugs, fractures and porous fault rocks. Although some Yijianfang Formation outcrops contain shallow (formed near surface) palaeokarst features, cores from the Halahatang oilfield lack penetrative palaeokarst evidence. Outcrop palaeokarst cavities and opening-mode fractures are mostly mineral filled but some show evidence of secondary dissolution and fault rocks are locally highly ( c . 30%) porous. Cores contain textural evidence of repeated formation of dissolution cavities and subsequent filling by cement. Calcite isotopic analyses indicate depths between c . 220 and 2000 m. Correlation of core and image logs shows abundant cement-filled vugs associated with decametre-scale fractured zones with open cavities that host hydrocarbons. A Sm–Nd isochron age of 400 ± 37 Ma for fracture-filling fluorite indicates that cavities in core formed and were partially cemented prior to the Carboniferous, predating Permian oil emplacement. Repeated creation and filling of vugs, timing constraints and the association of vugs with large cavities suggest dissolution related to fractures and faults. In the current high-strain-rate regime, corroborated by velocity gradient tensor analysis of global positioning system (GPS) data, rapid horizontal extension could promote connection of porous and/or solution-enlarged fault rock, fractures and cavities. Supplementary material: Stable isotopic analyses and the velocity gradient tensor and principal direction and magnitude calculation are available at https://doi.org/10.6084/m9.figshare.c.4946046 Thematic collection: This article is part of the The Geology of Fractured Reservoirs collection available at: https://www.lyellcollection.org/cc/the-geology-of-fractured-reservoirs

Geology↗

Purification of contaminated water by filtration through porous glass

Method for purifying water that is contaminated with mineral salts and soluble organic compounds is described. Method consists of high pressure filtration of contaminated water through stabilized porous glass membranes. Procedure for conducting filtration is described. Types of materials by percentage amounts removed from the water are identified.

Wydeven, T.↗

Temperature reference for microwave radiometer calibration

New temperature reference avoids need to physically remove antenna and replace it with calibrating termination. Device is piece of porous microwave absorber fitted with cap of nonporous plastic foam. Absorbent material is soaked with cryogen. Procedure ensures that temperature at which microwaves are absorbed is exactly that of cryogen.

Love, A. W.↗

A summary of porous tube plant nutrient delivery system investigations from 1985 to 1991

The Controlled Ecological Life Support System (CELSS) Program is a research effort to evaluate biological processes at a one person scale to provide air, water, and food for humans in closed environments for space habitation. This program focuses currently on the use of conventional crop plants and the use of hydroponic systems to grow them. Because conventional hydroponic systems are dependent on gravity to conduct solution flow, they cannot be used in the microgravity of space. Thus, there is a need for a system that will deliver water and nutrients to plant roots under microgravity conditions. The Plant Space Biology Program is interested in investigating the effect that the space environment has on the growth and development of plants. Thus, there is also a need to have a standard nutrient delivery method for growing plants in space for research into plant responses to microgravity. The Porous Tube Plant Nutrient Delivery System (PTPNDS) utilizes a hydrophilic, microporous material to control water and nutrient delivery to plant roots. It has been designed and analyzed to support plant growth independent of gravity and plans are progressing to test it in microgravity. It has been used successfully to grow food crops to maturity in an earth-bound laboratory. This document includes a bibliography and summary reports from the growth trials performed utilizing the PTPNDS.

Dreschel, T. W.↗

Hollow Fiber Space Suit Water Membrane Evaporator Development for Lunar Missions

The Space Suit Water Membrane Evaporator (SWME) is the baseline heat rejection technology selected for development for the Constellation lunar suit. The Hollow Fiber (HoFi) SWME is being considered for service in the Constellation Space Suit Element (CSSE) Portable Life Support Subsystem (PLSS) to provide cooling to the thermal loop through water evaporation to the vacuum of space. Previous work described the test methodology and planning to compare the test performance of three commercially available hollow fiber materials as alternatives to the sheet membrane prototype for SWME: 1) porous hydrophobic polypropylene, 2) porous hydrophobic polysulfone, and 3) ion exchange through nonporous hydrophilic modified Nafion. Contamination tests were performed to probe for sensitivities of the candidate SWME elements to organics and non-volative inorganics expected to be found in the target feedwater source, i.e., potable water provided by the vehicle. The resulting presence of precipitate in the coolant water could plug pores and tube channels and affect the SWME performance. From this prior work, a commercial porous hydrophobic hollow fiber was selected to satisfy both the sensitivity question and the need to provide 800 W of heat rejection. This paper describes the trade studies, the design methodology, and the hollow fiber test data used to design a full

Bue, Grant C.↗