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DOE OSTI2021

Rock weathering controls the potential for soil carbon storage at a continental scale

Abstract As rock-derived primary minerals weather to form soil, they create reactive, poorly crystalline minerals that bind and store organic carbon. By implication, the abundance of primary minerals in soil might influence the abundance of poorly crystalline minerals, and hence soil organic carbon storage. However, the link between primary mineral weathering, poorly crystalline minerals, and soil carbon has not been fully tested, particularly at large spatial scales. To close this knowledge gap, we designed a model that links primary mineral weathering rates to the geographic distribution of poorly crystalline minerals across the USA, and then used this model to evaluate the effect of rock weathering on soil organic carbon. We found that poorly crystalline minerals are most abundant and most strongly correlated with organic carbon in geographically limited zones that sustain enhanced weathering rates, where humid climate and abundant primary minerals co-occur. This finding confirms that rock weathering alters soil mineralogy to enhance soil organic carbon storage at continental scales, but also indicates that the influence of active weathering on soil carbon storage is limited by low weathering rates across vast areas.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Post-process annealing of large-scale 3D printed polyphenylene sulfide composites

Large-scale extrusion-based additive manufacturing of high-performance thermoplastic composites like fiber reinforced polyphenylene sulfide (PPS) is well-suited for tooling applications to lower manufacturing costs and lead times. Autoclave tooling requires good mechanical performance at temperatures even above the glass transition temperature (T g ). In this work, the authors have investigated a post-process isothermal annealing technique to improve the mechanical properties of various grades of carbon fiber reinforced PPS components printed on the Big Area Additive Manufacturing (BAAM) system. Since PPS is a semi-crystalline polymer, crystallinity can change during annealing and affect the mechanical properties of the part. In addition, isothermal annealing can also lead to solid-state structural changes in the form of thermal and oxidative branching and/or crosslinking reactions in some grades of PPS which can alter the crystallization process. This work reports the effect of annealing on dynamic mechanical properties of BAAM printed components, along with studies to determine the effect of annealing on crystallinity and the occurrence of oxidative reactions. Results showed that isothermal annealing at 250 °C for 18 h improved the storage modulus of all selected grades (neat and reinforced) of PPS at temperatures above T g . Annealing led to an overall increase in the degree of crystallinity, with secondary crystallization taking place. Although oxidative structural changes were observed to occur more on the surface of the PPS parts, they primarily influenced the size of crystals formed and did not significantly alter the degree of crystallinity at various regions within the sample.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Ultrasonic-Assisted Extrusion Processing for Enhancing Physical Properties of High-Density Polyethylene by Flow-Induced Crystallization

The evolution of crystallinity resulting from stress imposed on a melt, known as flow-induced crystallinity, can strongly influence the mechanical and physical properties of semicrystalline polymers. This study investigates shear-induced crystallization by applying an ultrasonic field to the melt flow as it passes through dies with various geometries. A custom-built sonication die is employed for controlling the dynamic temperature and shear environment, resulting in molecular alignment and potential for flow-induced crystallization. Application of both conventional and ultrasonic shear rates at the equilibrium melt temperature of high-density polyethylene (HDPE) was investigated to accelerate crystallinity and manipulate the crystal morphology across the film in pursuit of improved mechanical and gas barrier properties without the need for additives or other polymer layers. The relationships among ultrasonic-assisted extrusion processing, polymer structure, and performance were analyzed using wide- and small-angle X-ray scattering (WAXS and SAXS), tensile testing, and oxygen transmission rate (OTR) analysis. Multiple linear regression models were implemented to predict the correlation among HDPE structure, process, and properties. Structural analysis revealed that both conventional and ultrasonic shear rates had the most significant influence on lamellar spacing and redistribution of rigid and soft amorphous fractions within the crystalline domains, ultimately dictating the mechanical and physical properties of the films. The goal is to explore the potential of the ultrasonic-assisted high crystallinity monolayer that can replace some of the functionality of complex, heterogeneous multilayer packaging with a single-material film having enhanced oxygen barrier properties.

crystallinity↗

DOE OSTI2020

Dynamic behavior of reversible oxygen migration in irradiated-annealed high temperature superconducting wires

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2025

A Spatially Resolved Evaluation of Accelerated Environmental Aging on Emerging Polypropylene-Based Photovoltaic Backsheets Using Raman Spectroscopy

For this work, accelerated aging was used to assess environmental degradation in emerging co-extruded polypropylene (PP)-based backsheets under three different environmental conditions (65°C/20% relative humidity (RH), 75°C/20% RH, and 75°C/50% RH). Although differential scanning calorimetry did not measure crystallinity changes with exposure, spatially resolved Raman spectroscopy identified crystallinity increases in the core layer of aged samples, indicating a heterogeneous postcrystallization process. The Raman results were in agreement with synchrotron-based microfocused wide-angle X-ray scattering measurements. Cross-sectional nanoindentation was used to correlate localized crystallinity shifts with changes in Young's modulus. A similar trend was found where increased modulus was measured in the core layer, supporting the relationship between modulus and crystallinity. Finally, dielectric characterization was used to assess the impact of these material property changes on performance. While changes in the backsheet material properties and dielectric performance were observed with accelerated aging, these shifts generally equilibrated with time, indicating overall stability in response to environmental stressors. Additionally, the identified heterogeneous material property changes indicate that spatially resolved crystallinity measurements may be a valuable early failure indicator to be used in the assessment of PV backsheet long-term durability.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Why Seeding Works When Nucleation Barriers Vanish

Crystallization is a process governed by the interplay between nucleation and growth. While crystalline seeds are known to reduce nucleation barriers and accelerate crystallization under nucleation-limited conditions, their influence when nucleation is not the limiting step remains poorly understood. This creates a mechanistic puzzle in systems where nucleation barriers are already negligible, yet seeding still accelerates crystallization. Here, the synthesis of zeolites is a quintessential example of growth-limited crystallization in which seeds accelerate the process despite negligible homogeneous nucleation barriers. Using coarse-grained molecular dynamics simulations─validated across two zeolites and the unrelated case of ice crystallization─we establish that growth-limited crystallization produces many small, misoriented crystallites whose slow coarsening into larger domains controls the emergence of X-ray-detectable crystallinity. Local crystalline order, structural coherence, and X-ray detectability are therefore kinetically decoupled milestones: the first can be reached rapidly while the latter two lag significantly. Seeds resolve this lag by imposing a common orientational registry on nascent crystallites, enabling their coherent coalescence into large seed-bound domains. This early coherence-building step produces a crystallite-size asymmetry that accelerates subsequent coarsening, advancing the onset of X-ray-detectable crystallinity without necessarily increasing the nucleated fraction. We conclude that under growth-limited conditions, the apparent induction period observed in powder X-ray diffraction reflects the time required to build long-range coherence, not the time to form crystalline material. Accordingly, seeds function not primarily by reducing nucleation barriers but by enforcing spatial coherence, thereby shortening the time required to develop long-range order detectable by X-ray diffraction.

Growth-Limited Crystallization↗

DOE OSTI2021

Two-bond 13 C– 13 C spin-coupling constants in saccharides: dependencies on exocyclic hydroxyl group conformation

Seven doubly 13 C-labeled isotopomers of methyl β-D-glucopyranoside, methyl β-D-xylopyranoside, methyl β-D-galactopyranoside, methyl β-D-galactopyranosyl-(1→4)-β-D-glucopyranoside and methyl β-D-galactopyranosyl-(1→4)-β-D-xylopyranoside were prepared, crystallized, and studied by single-crystal X-ray crystallography and solid-state 13 C NMR spectroscopy to determine experimentally the dependence of 2 J C1,C3 values in aldopyranosyl rings on the C1–C2–O2–H torsion angle, θ 2 , involving the C2 carbon of the C1–C2–C3 coupling pathway. Using X-ray crystal structures to determine θ 2 in crystalline samples and by selecting compounds that exhibit a relatively wide range of θ 2 values in the crystalline state, 2 J C1,C3 values measured in crystalline samples were plotted against θ 2 and the resulting plot compared to that obtained from density functional theory (DFT) calculations. For θ 2 values ranging from ~90° to ~240°, very good agreement was observed between the experimental and theoretical plots, providing strong validation of DFT-calculated spin-coupling dependencies on exocyclic C–O bond conformation involving the central carbon of geminal C–C–C coupling pathways. we report that these findings provide new experimental evidence supporting the use of 2 J CCC values as non-conventional spin-coupling constraints in MA'AT conformational modeling of saccharides in solution, and the use of NMR spin-couplings not involving coupled hydroxyl hydrogens as indirect probes of C–O bond conformation. Solvomorphism was observed in crystalline βGal-(1→4)-βGlcOCH 3 wherein the previously-reported methanol solvate form was found to spontaneously convert to a monohydrate upon air-drying, leading to small but discernible conformational changes in, and a new crystalline form of, this disaccharide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Low-temperature MnBi alloys: Electronic and magnetic properties, constitution, morphology and fabrication (Review article)

The article reviews the rich phenomena of physical properties of MnBi. The diverse phenomena include strong spin-orbit interaction, anomalous temperature dependence of the coercivity and the magneto-crystalline anisotropy field, unique magneto-optical properties. Issues addressed include the nature of the electronic ground states of MnBi, the electronic and magnetic structures, Fermi surface, magneto-crystalline anisotropy, x-ray magnetic dichroism. The discussion includes key experiments, such as optical and magneto-optical spectroscopic measurements, de Haas-van Alphen (dHvA) measurements, x-ray photoemission and x-ray absorption spectroscopy measurements as well as x-ray magnetic circular dichroism. The effect of the spin-orbit (SO) interaction and Coulomb repulsion U were found to be crucial for the Fermi surface, cyclotron masses, magneto-optical properties, and x-ray magnetic circular dichroism. The microscopic origin of unique magneto-crystalline anisotropy and giant Kerr effect in MnBi is analyzed in detail. The huge Kerr effect in MnBi is caused by the combination of a sizable magnetic moment on manganese, the large spin-orbit coupling of bismuth, and a strong hybridization between the manganese 3d and the bismuth 6p states. The magneto-optically active states are mainly the 6p states of Bi. We show that the observed temperature dependence of the magneto-crystalline anisotropy can be explained taking into account the spin-orbit interaction together with strong Coulomb electron-electron interaction. The SO coupling of Bi is equally responsible for the large magneto-crystalline anisotropy energy as is the exchange splitting of Mn. The fabrication, morphology, and constitution of low-temperature MnBi alloys in bulk, thin films, and nanoparticles are discussed. The nanocomposite permanent magnetic materials based on MnBi, (Co, Fe) and Nd 2 Fe 14 B are also discussed.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Local structure of zinc–indium–tin oxide films via grazing-incidence x-ray pair-distribution functions and theoretical methods

A detailed experimental and theoretical study on the local (r ≤ 4.5 Å) atomic structure of amorphous and crystalline zinc–indium–tin oxide (ZITO) thin films using grazing-incidence x-ray Pair-Distribution Functions (PDFs), ab initio Molecular Dynamics (MD), and Empirical Potential Structure Refinement (EPSR) Monte Carlo simulations is presented. High-energy synchrotron x rays, a two-dimensional detector, and different incident angles were used to probe the depth uniformity of five (ZnO) 0.15 (In 2 O 3 ) 0.70 (SnO 2 ) 0.15 films that were deposited via pulsed-laser deposition at growth temperatures (T G ) ranging from 25 to 300 °C. Films deposited at T G ≤ 150 °C were amorphous. The partially crystalline (T G = 200 °C) and fully crystalline (T G = 300 °C) films were highly textured. Both crystalline and amorphous structures were investigated using ab initio MD and EPSR Monte Carlo simulations. The density of the amorphous films determined from the experimental data agreed with MD calculations. Coordination numbers, bond lengths, and distortion for metal–oxygen and for both the edge- and corner-shared In–metal shells up to 4.5 Å obtained from PDF analysis closely agreed with MD and EPSR simulations. There is a pronounced decrease in the edge- and corner-shared In–Zn distances arising from the shorter Zn–O bond length, Zn–O tetrahedral coordination, and In–O–Zn angle in amorphous ZITO compared to its crystalline counterpart. A maximum in electrical mobility was observed for the amorphous film just before crystallization occurred. While the peak is broad, consistent with nearly unchanged overall cation–oxygen coordination in the amorphous films, ESPR results indicate that the tetrahedral coordination follows the conductivity trend.

Grazing Incidence X-ray↗

DOE OSTI2022

Dynamically tunable second-harmonic generation using hybrid nanostructures incorporating phase-change chalcogenides

Nonlinear metasurfaces with high conversion efficiencies have been vastly investigated. However, strong dynamic tunability of such devices is limited in conventional passive plasmonic and dielectric material platforms. Germanium antimony telluride (GST) is a promising phase-change chalcogenide for the reconfiguration of metamaterials due to strong nonvolatile changes of the real and imaginary parts of the refraction index through amorphous-crystalline phase change. The orderly structured GST has an even higher potential in tunable second-harmonic generation (SHG) with a non-centrosymmetric crystal structure at the crystalline phase, while the amorphous phase of GST does not exhibit bulk second-order nonlinearity. Here, we experimentally demonstrate SHG switches by actively controlling the crystalline phase of GST for a GST-based hybrid metasurface featuring a gap-surface plasmon resonance, and a quarter-wave asymmetric Fabry–Perot (F–P) cavity incorporating GST. We obtain SHG switches with modulation depths as high as ~ 20 dB for the wavelengths at the on-state resonance. We also demonstrate the feasibility of multi-level SHG modulation by leveraging three controlled GST phases, i.e., amorphous, semi-crystalline, and crystalline, for the gap-surface plasmon hybrid device, which features stronger light–matter interaction and has higher resonant SHG efficiencies than the asymmetric F–P cavity device at respective GST phases. This research reveals that GST-based dynamic SHG switches can be potentially employed in practical applications, such as microscopy, optical communication, and photonic computing in the nonlinear regime.

42 ENGINEERING↗

DOE OSTI2023

Challenges in correlating oxygen stable isotope ratios of hydrates on uranium ore concentrates to process waters

Exchange of oxygen stable isotopes (δ 18 O values) between precipitation waters and uranium oxides is governed by thermodynamics or kinetics. It has been assumed that meteoric waters can be related to precipitation waters in uranium ore concentrates and their calcination and reduced uranium oxide products. With this assumption, the δ 18 O values of uranium materials could provide forensic signatures that identify the production history and geolocation of nuclear materials. To further exploit the potential of δ 18 O values in nuclear material analysis, this study examines the oxygen stable isotope exchange in two UOCs, magnesium diuranate (MDU) and sodium diuranate (SDU). MDU and SDU were synthesized from solutions of uranyl nitrate hexahydrate using precipitation waters with unique oxygen isotope compositions. The structures of the MDU and SDU were analyzed using powder X-ray diffraction (p-XRD) and thermal mass loss curves, while the δ 18 O values of waters generated during thermal decomposition were analyzed using a thermogravimetric analyzer coupled to an isotope ratio infrared spectrometer (TGA-IRIS). By p-XRD, the MDU was uniform and amorphous across all syntheses with residual crystalline material incorporated as a minor component. Combined with the TGA results, all of the MDU is likely amorphous MgU 2 O 7 ·3H 2 O with MgO impurities present throughout. In contrast, the SDU synthesis resulted in multiple phases with many samples exhibiting crystalline phases including a combination of Na(UO 2 ) 4 O 2 (OH) 5 ·5H 2 O and Na 2 (UO2) 6 O 4 (OH) 6 ·8H 2 O with a Na 2 U 2 O 7 minor phase. A small fraction of the SDU samples were amorphous with no crystalline XRD peaks observed. Mass loss curves of the SDU samples revealed that the amorphous samples contained inclusions of similar crystalline phases compared to the crystalline materials. The uniformity of the MDU samples enabled highly reproducible measurements of δ 18 O values of the water vapor yielded for two dehydration events at 170 °C and 500 °C. In contrast, the multiphase composition of the SDU samples resulted in poor reproducibility in δ 18 O values. In conclusion, neither system revealed any correlation between the δ 18 O values of precipitation water, and the waters released during dehydration of the UOCs.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2020

Toward non-Si electronics: From remote epitaxy to layer splitting of 2D materials for mixed dimensional heterostructures

The current electronics has been mainly dominated by Si-based devices due to their mature processing system and exceptional cost-effectiveness. However, next generation electronics needs novel functionalities that cannot be realized by Si because of intrinsic limitation of Si. Accordingly, demand for non-Si electronics has been getting substantially high. Unfortunately, current methodology requires extremely high cost for non-Si materials, which impedes the progress in developing the non-Si based electronics. Here, I will discuss about our group’s efforts to address this issue. Our team recently conceived a new crystalline growth, termed as “remote epitaxy”, which can copy/paste crystalline information from substrates remotely through graphene, thus generating single-crystalline films on graphene. As interfacial binding energy is attenuated by inserting graphene at interface, the single-crystalline films can be easily exfoliated from the slippery graphene surface. Also, the graphene-coated substrates can be, in principle, reused infinitely to produce single-crystalline films. Thus, the remote epitaxy can produce non-Si semiconductor films with unprecedented cost efficiency while allowing additional flexible device functionality required for current ubiquitous electronics. Next, I will discuss about a layer splitting technique which can be a potential solution to overcome the problem in obtaining large-scale and monolayer 2D materials. A 2D material-based heterostructure has been intensively studied because of its unique device functionalities and novel physics. However, it is extremely challenging to secure large-scale and monolayer 2D materials because of following issues: 1) poor scalability for laboratory fabrication processes of 2D heterostructures and 2) lack of well-defined control parameters for kinetics of 2D materials and predictable number of layers of 2D materials. To resolve this issue, we conceived a new approach called “layer-resolved splitting” which obtains multiple monolayer from multilayer 2D materials by controlling interfacial toughness contrast. As this method is versatile and universal, we can, in principle, apply to all 2D materials. We succeeded in having large-scale, monolayer 2D materials through our approach and, thereby 2D heterostructures were demonstrated for functional devices. Lastly, I would like to discuss opportunities of mixed-dimensional heterostructure demonstrated by remote epitaxy and layer-resolved splitting. As they produce freestanding 3D bulk films and 2D atomic layers, a new type of 3D/2D heterostructures can be realized where a new physics and new device architecture are revealed. Therefore, I believe that a new opportunity will be discovered through the mixed-dimensional heterostructures.

Bae, Sang-Hoon↗

DOE OSTI2022

Advanced Heterogeneous Integration Enabled by 3D Freestanding Membranes—From Material Growths to Applications

For the future of electronics such as bioelectronics, 3D integrated electronics, and bendable electronics, the need for flexibility and stackability of electronic products has substantially grown up. However, conventional wafer-based single-crystalline semiconductors cannot catch up with such trends because they are bound to thick rigid wafers such that they are neither flexible nor stackable. Although polymer-based organic electronic materials are more compatible as they are mechanically compliant and less costly than inorganic counterparts, their electronic/photonic performance is substantially inferior to that of single-crystalline inorganic materials. Such performance-mechanical compliance dilemma could be resolved by developing methods to obtain cheap, flexible, stackable, single-crystalline inorganic systems. Such dream electronic systems could be realized by producing single-crystalline freestanding membranes. For the past few decades, various layer transfer techniques (a.k.a layer liftoff techniques) have been developed to produce single-crystalline freestanding membranes. In today's talk, I will present the survey of the layer liftoff techniques and go over how these strategies unlock new ways of manufacturing advanced electronic systems. In addition, I will introduce unprecedented artificial heterostructure devices enabled by stacking of those freestanding 3D material membranes, e.g., the world's smallest vertically-stacked full-color micro-LEDs, the world's best multiferroic devices, chip-less wireless e-skin, and reconfigurable hetero-integrated chips with AI accelerators.

Kim, Jeehwan↗

DOE OSTI2022

Advanced Heterogeneous Integration Enabled by 3D Freestanding Membranes—From Material Growths to Applications

Kim, Jeehwan↗

DOE OSTI2022

2D material-based layer transfer: Challenges and opportunities

For future of electronics such as bioelectronics, 3D integrated electronics, and bendable electronics, needs for flexibility and stackability of electronic products have substantially grown up. However, conventional wafer-based single-crystalline semiconductors cannot catch up with such trends because they are bound to the thick rigid wafers such that they are neither flexible nor stackable. Although polymer-based organic electronic materials are more compatible as they are mechanically complaint and less costly than inorganic counterparts, their electronic/photonic performance is substantially inferior to that of single-crystalline inorganic materials. For the past few decades, many different strategies to mitigate such performance-mechanical compliance dilemma by developing methods to obtain cheap, flexible, stackable, single-crystalline inorganic systems. In today’s talk, I will discuss about various strategies to realize such a dream electronic system and how these strategies unlock new ways of manufacturing advanced electronic systems. One of the most promising approaches is to fabricate freestanding ultrathin membranes from existing functional material wafers by peeling the active layers from the top. I will overview all freestanding membrane methods and especially dive deeply into 2D materials-based layer transfer (2DLT) technique that has been recently emerging as one of the very promising options. In the 2DLT process, one can produce single-crystalline freestanding membranes from 3D materials by performing remote epitaxy or van der Waals epitaxy on 2D materials followed by peeling active single-crystalline films from the 2D materials. I will discuss about the challenges and opportunities of this technology. In addition, I will present unprecedented artificial heterostructures that can be enabled by stacking those freestanding 3D material membranes.

Kim, Jeehwan↗

DOE OSTI2026

Why Seeding Works When Nucleation Barriers Vanish

This paper explains why seeds can speed up crystallization even when the formation of new crystal nuclei is not the slow step. In zeolite synthesis, local crystalline order can form relatively early, but the material may still appear poorly crystalline by X-ray diffraction because many small crystallites are misoriented and lack long-range coherence. Using coarse-grained molecular simulations, the study showed that seeds help solve this coherence problem. Rather than primarily lowering a nucleation barrier, seeds impose a common orientation on nearby growing crystallites, allowing them to merge into larger, better aligned domains. This accelerates the development of X-ray-detectable crystallinity even if the total amount of locally ordered material has not changed much. The work changes how induction times in zeolite synthesis should be interpreted: the delay before X-ray crystallinity appears can reflect the time needed to build long-range structural coherence, not simply the time needed to form crystalline material. This provides a new explanation for why seeding is effective in growth-limited crystallization and offers design principles for controlling crystallization rate and crystal quality.

36 MATERIALS SCIENCE↗

NASA NTRS2000

The Formation Age of Comets: Predicted Physical and Chemical Trends

Dust grains in Herbig Ae/Be stars are continuously replenished by infalling comets. The IR spectra of these cometary grains appear to evolve temporally from initially amorphous astronomical silicates in young protostars to crystalline olivine in much older sources. Crystalline olivine can only be produced from amorphous silicates on a time scale of months-to-years via thermal annealing at temperatures near 1000 K. Since such sustained high temperatures only occur near the central star, dust annealed at 1000 K in inner nebular regions must be continuously transported beyond the nebular snowline to be incorporated into the next generation of cometesimals. The average formation age of a comet can therefore be measured as a ratio of the annealed crystalline olivine dust component to the total dust content of the comet. Comets formed from nearly pristine interstellar materials early in the protostellar nebula stage will contain very little crystalline dust whereas comets formed towards the end of the accretion period will incorporate a much higher percentage of annealed silicate. It is unlikely that only dust grains circulate from the inner to the outer nebula; the gas associated with such dust should also find its way beyond the snowline. Since this gas and dust will have equilibrated in the higher pressure-temperature regime of the inner nebula, it will contain a much higher proportion of hydrocarbons and ammonia than more pristine interstellar ices. Therefore, in addition to a higher fraction of crystalline dust, later forming comets should also contain higher ratios of hydrocarbons to CO and ammonia to N2 than do those formed early in the history of the nebula.

Nuth, Joseph A., III↗

NASA NTRS1995

The Metastable Persistence of Vapor-Deposited Amorphous Ice at Anomalously High Temperatures

Studies of the gas release, vaporization behavior and infrared (IR) spectral properties of amorphous and crystalline water ice have direct application to cometary and planetary outgassing phenomena and contribute to an understanding of the physical properties of astrophysical ices. Several investigators report anomalous phenomena related to the warming of vapor-deposited astrophysical ice analogs. However gas release, ice volatilization and IR spectral features are secondary or tertiary manifestations of ice structure or morphology. These observations are useful in mimicking the bulk physical and chemical phenomena taking place in cometary and other extraterrestrial ices but do not directly reveal the structural changes which are their root cause. The phenomenological interpretation of spectral and gas release data is probably the cause of somewhat contradictory explanations invoked to account for differences in water ice behavior in similar temperature regimes. It is the microstructure, micromorphology and microchemical heterogeneity of astrophysical ices which must be characterized if the mechanisms underlying the observed phenomena are to be understood. We have been using a modified Transmission Electron Microscope to characterize the structure of vapor-deposited astrophysical ice analogs as a function of their deposition, temperature history and composition. For the present experiments, pure water vapor is deposited at high vacuum onto a 15 K amorphous carbon film inside an Hitachi H-500H TEM. The resulting ice film (approx. 0.05 micrometers thick) is warmed at the rate of 1 K per minute and diffraction patterns are collected at 1 K intervals. These patterns are converted into radial intensity distributions which are calibrated using patterns of crystalline gold deposited on a small part of the carbon substrate. The small intensity contributed by the amorphous substrate is removed by background subtraction. The proportions of amorphous and crystalline material in each pattern are determined by subtracting a percentage of crystalline component relative to amorphous and pure crystalline endmembers. Vapor-deposited water ice undergoes two amorphous to amorphous structural transformations in the temperature range 15-130 K with important astrophysical implications. The onset of cubic crystallization occurs at 142-160 K (at 1K per minute heating rates) during which the 220 and 311 diffraction maxima appear and 0.1 micrometer crystallites can be seen in bright field images. This transition is time dependent.

Blake, David F.↗