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Evaluation of Student Outcomes in Materials Science and Technology

This paper specifies 14 benchmarks and exit standards for the introduction of Materials Science and Technology in a secondary school education. Included is the standard that students should be able to name an example of each category of technological materials including metals, glass/ceramics, polymers (plastics) and composites. Students should know that each type of solid material has specific properties that can be measured. Students will learn that all solid materials have either a long range crystalline structure or a short range amorphous structure (i.e., glassy). They should learn the choice of materials for a particular application depends on the properties of the material, and the properties of the material depends on its crystal structure and microstructure. The microstructure may be modified by the methods by which the material is processed; students should explain this by the example of sintering a ceramic body to reduce its porosity and increase its densification and strength. Students will receive exposure to the world of work, post secondary educational opportunities, and in general a learning that will lead to a technologically literate intelligent citizen.

Piippo, Steven

A family of dual-anion-based sodium superionic conductors for all-solid-state sodium-ion batteries

The sodium (Na) superionic conductor is a key component that could revolutionize the energy density and safety of conventional Na-ion batteries. However, existing Na superionic conductors are primarily based on a single-anion framework, each presenting inherent advantages and disadvantages. Here we introduce a family of amorphous Na-ion conductors (Na 2 O 2 –MCl y , M = Hf, Zr and Ta) based on the dual-anion framework of oxychloride. Benefiting from a dual-anion chemistry and with the resulting distinctive structures, Na 2 O 2 –MCl y electrolytes exhibit room-temperature ionic conductivities up to 2.0 mS cm -1 , wide electrochemical stability windows and desirable mechanical properties. All-solid-state Na-ion batteries incorporating amorphous Na 2 O 2 –HfCl 4 electrolyte and a Na 0.85 Mn 0.5 Ni 0.4 Fe 0.1 O 2 cathode exhibit a superior rate capability and long-term cycle stability, with 78% capacity retention after 700 cycles under 0.2 C (1C = 120 mA g -1 ) at room temperature. The discoveries in this work could trigger a new wave of enthusiasm for exploring new superionic conductors beyond those based on a single-anion framework.

25 ENERGY STORAGE

Effect of Post-HALT Annealing on Leakage Currents in Solid Tantalum Capacitors

Degradation of leakage currents is often observed during life testing of tantalum capacitors and is sometimes attributed to the field-induced crystallization in amorphous anodic tantalum pentoxide dielectrics. However, degradation of leakage currents and the possibility of annealing of degraded capacitors have not been investigated yet. In this work the effect of annealing after highly accelerated life testing (HALT) on leakage currents in various types of solid tantalum capacitors was analyzed. Variations of leakage currents with time during annealing at temperatures from 125 oC to 180 oC, thermally stimulated depolarization (TSD) currents, and I-V characteristics were measured to understand the conduction mechanism and the reason for current degradation. Annealing resulted in a gradual decrease of leakage currents and restored their initial values. Repeat HALT after annealing resulted in reproducible degradation of leakage currents. The observed results are explained based on ionic charge instability (drift/diffusion of oxygen vacancies) in the tantalum pentoxide dielectrics using a modified Schottky conduction mechanism.

Teverovsky, Alexander

Salt Distribution from Freezing Intrusions in Ice Shells on Ocean Worlds: Application to Europa

Several icy moons and dwarf planets appear to have hosted subsurface liquid water. Liquid water intruding upwards into the icy outer shells of these worlds freezes, forming ice and (from ocean solutes) non-ice solids. Here, we model concentrated aqueous solutions below 273 K to simulate the compositional evolution of freezing spherical intrusions. Starting solutions are based on five previously reported compositional end members for Europa's ocean. For moderate-pH end members dominated by chloride, sulfate, and/or carbonate, the solids formed include Ca-, Mg-, and Na-sulfates and -carbonates, as well as Na- and K-chlorides. For silica-rich, high-pH end members, abundant amorphous silica forms with, potentially, similarly abundant NaOH and KOH. We further develop a new numerical model to compute the spatial distribution of the formed solids and residual brine as freezing progresses. If non-ice solids settle to the bottom, their deposits tend to have stacked hourglass shapes, widening each time the crystallization temperature of a new solid is reached. We discuss the applicability of this model to vertical fractures and global freezing of a subsurface ocean. These results inform (i) how compositional heterogeneities may affect the thermophysical properties of ice shells, which in turn influence convective and cryovolcanic transport, (ii) the compatibility of brine pockets with physicochemical conditions suitable for microbial life, and (iii) possible measurements of compositional heterogeneities within ice shells by spacecraft such as NASA's Europa Clipper and ESA's JUICE missions. The methodology developed here is applicable to other ice-covered ocean worlds.

Planetary structure

4 V Na Solid State Batteries Enabled by a Scalable Sodium Metal Oxyhalide Solid Electrolyte

All-solid-state sodium batteries (ASSSBs) are viable candidates for large scale energy storage that could vie with lithium. Ductile solid catholytes for such cells that can be prepared without extensive ball milling and directly paired with high voltage sodium cathodes are lacking, however. We report a new amorphous fast Na-ion conducting metal oxychloride that meets these criteria, synthesized through a scalable and low-cost route based on a spontaneous solid-state reaction with simple short mixing and 100 °C annealing. It has an ionic conductivity of 1.2 mS·cm–1 and low activation energy of 0.31 eV. Due to its dual O2–/Cl– framework, it exhibits a high anodic potential of 4 V vs Na+/Na and good chemical/electrochemical compatibility with high voltage sodium cathode materials. ASSSBs consisting of the oxychloride solid electrolyte paired with a high voltage P2–Na2/3Ni1/3Mn2/3O2 cathode showed stable long-term cycling with a 4.0 V vs Na3Sn cutoff potential and even to 4.3 V.

solid-state electrolyte, solid-state batteries, Nu

Graphene Based Ultra-Capacitors for Safer, More Efficient Energy Storage

Current power storage methods must be continuously improved in order to keep up with the increasingly competitive electronics industry. This technological advancement is also essential for the continuation of deep space exploration. Today's energy storage industry relies heavily on the use of dangerous and corrosive chemicals such as lithium and phosphoric acid. These chemicals can prove hazardous to the user if the device is ruptured. Similarly they can damage the environment if they are disposed of improperly. A safer, more efficient alternative is needed across a wide range of NASA missions. One solution would a solid-state carbon based energy storage device. Carbon is a safer, less environmentally hazardous alternative to current energy storage materials. Using the amorphous carbon nanostructure, graphene, this idea of a safer portable energy is possible. Graphene was electrochemically produced in the lab and several coin cell devices were built this summer to create a working prototype of a solid-state graphene battery.

Composite battery

Non-stoichiometry Governs the Pathway from Amorphous to Crystalline Calcium Carbonate

The controlled crystallization of calcium carbonate underlies the elaborate architectures of marine corals, the design of biomimetic materials, and the global carbon cycle. Despite its ubiquity, the chemical mechanisms that govern the crystallization of calcium carbonate from its amorphous precursor, amorphous calcium carbonate (ACC), remain elusive, largely due to the difficulty in resolving the structure and chemistry of this transient amorphous state. Here, we use time-lapse photography, image analysis, spatially resolved pH determination, in situ synchrotron pair distribution function (PDF) analysis, and dynamic nuclear polarization (DNP) solid-state nuclear magnetic resonance (NMR) spectroscopy to reveal pervasive compositional variability in ACC that underpins its metastability and crystallization. By evaluating the kinetics of the amorphous-to-crystalline transition across different solution chemistries, we demonstrate that ACC is non-stoichiometric and CO 3 -deficient. Counterions from the precursor (e.g., NO 3 - from Ca(NO 3 ) 2 ) substitute into the ACC network, displacing CO 3 ions and mediating both ACC stability and transformation. Crystallization proceeds through refinement of the stoichiometry toward CaCO 3 and uptake of free CO 3 2- anions. Furthermore, these findings are consistent across a wide range of concentrations and different carbonate sources, explaining the diverse behaviors observed for ACC and providing a chemical framework for controlling calcium carbonate crystallization.

77 NANOSCIENCE AND NANOTECHNOLOGY

CO 2 Uptake and Stability Enhancement in Vinyltrimethoxysilane‐Treated SBA‐15 Solid Amine‐Based Sorbents

Abstract Silica‐supported amine absorbents, including materials produced by tethering aminosilanes or infusion of poly(ethyleneimine), represent a promising class of materials for CO 2 capture applications, including direct air and point source capture. Various silica surface treatments and functionalization strategies are explored to enhance stability and CO 2 uptake in amine‐based solid sorbent systems. Here, the synthesis and characterization of novel vinyltrimethoxysilane‐treated Santa Barbara Amorphous‐15 (SBA‐15) supports and the corresponding enhancement in CO 2 uptake compared to various SBA‐15‐based control supports are presented. The relationship between CO 2 diffusion and amine efficiency in these systems is explored using a previously reported kinetic model. The synthesized materials are characterized with CO 2 and H 2 O isotherms, diffuse reflectance infrared Fourier transform spectroscopy, 1 H T 1 – T 2 relaxation correlation NMR, and rapid thermal cycling experiments. The novel support materials are shown to enable high amine efficiencies, approaching a fourfold improvement over standard SBA‐15‐supported amines, while simultaneously exhibiting excellent stability when cycled rapidly under humid conditions. As the poly(ethyleneimine) loadings are held constant across the various samples, enhancements in CO 2 uptake are attributed to differences in the way the poly(ethyleneimine) interacts with the support surface.

Vallace, Anthony

Controlled patterning of crystalline domains by frontal polymerization

Materials with hierarchical architectures that combine soft and hard material domains with coalesced interfaces possess superior properties compared with their homogeneous counterparts. These architectures in synthetic materials have been achieved through deterministic manufacturing strategies such as 3D printing, which require an a priori design and active intervention throughout the process to achieve architectures spanning multiple length scales. Here we harness frontal polymerization spin mode dynamics to autonomously fabricate patterned crystalline domains in poly(cyclooctadiene) with multiscale organization. This rapid, dissipative processing method leads to the formation of amorphous and semi-crystalline domains emerging from the internal interfaces generated between the solid polymer and the propagating cure front. The size, spacing and arrangement of the domains are controlled by the interplay between the reaction kinetics, thermochemistry and boundary conditions. Small perturbations in the fabrication conditions reproducibly lead to remarkable changes in the patterned microstructure and the resulting strength, elastic modulus and toughness of the polymer. Furthermore, this ability to control mechanical properties and performance solely through the initial conditions and the mode of front propagation represents a marked advancement in the design and manufacturing of advanced multiscale materials. Drawing inspiration from biological systems in which structural complexity develops through dissipative reaction–diffusion processes, this study explores a transformative synthetic manufacturing strategy aimed at harnessing the principles underpinning morphogenic growth, unlocking new avenues for advanced materials design and fabrication. Synthetic coupled reaction-transport processes offer a versatile yet relatively underexplored method to manipulate the spatial attributes of synthetic materials10. Here we introduce an innovative manufacturing approach based on frontal ring-opening metathesis polymerization (FROMP) that draws parallels with morphogenic growth and development, enabling the formation of patterned microstructures within polymeric materials.

36 MATERIALS SCIENCE

Physical Properties of Centaur Objects

Centaurs are objects in unstable orbits that cross the orbits of the giant planets. They are presumed to be recent additions to the planetary zone of the Solar System, having been dynamically perturbed from the Kulper Disk by the gravitational action of Neptune. Telescopic observations of Centaurs are important because they give us a view of the composition (and in some cases cometary activity) of large bodies that are normally to far from the Sun to be studied in detail. This paper reports on physical observations, primarily through spectroscopy, of the compositions of a small number of Centaurs that have been studied to date. In particular, the composition of 5145 Pholus is reviewed, following the published work of Crulkshank et al., in which compositional models that fit the spectrum well included H2O ice, the organic solid Titan tholin, a light hydrocarbon ice (e.g., CH3OH), the silicate mineral olivine, and amorphous carbon. The Centaur 1997 CU(26) shows evidence for H2O ice, but nothing else is yet identified.

Cruikshank, Dale P.

Titan haze: structure and properties of cyanoacetylene and cyanoacetylene-acetylene photopolymers

The structure and morphological properties of polymers produced photochemically from the UV irradiation of cyanoacetylene and cyanoacetylene mixtures have been examined to evaluate their possible contribution to the haze layers found on Titan. A structural analysis of these polymers may contribute to our understanding of the data returned from the Huygens probe of the Cassini mission that will pass through the atmosphere of Titan in the year 2004. Infrared analysis, elemental analysis, and thermal methods (thermogravimetric analysis, thermolysis, pyrolysis) were used to examine structures of polycyanoacetylenes produced by irradiation of the gas phase HC3N at 185 and 254 nm. The resulting brown to black polymer, which exists as small particles, is believed to be a branched chain of conjugated carbon-carbon double bonds, which, on exposure to heat, cyclizes to form a graphitic structure. Similar methods of analysis were used to show that when HC3N is photolyzed in the presence of Titan's other atmospheric constituents (CH4, C2H6, C2H2, and CO), a copolymer is formed in which the added gases are incorporated as substituents on the polymer chain. Of special significance is the copolymer of HC3N and acetylene (C2H2). Even in experiments where C2H2 was absorbing nearly all of the incident photons, the ratio of C2H2 to HC3N found in the resulting polymer was only 2:1. Scanning electron microscopy was used to visually examine the polymer particles. While pure polyacetylene particles are amorphous spheres roughly 1 micrometer in diameter, polycyanoacetylenes appear to be strands of rough, solid particles slightly smaller in size. The copolymer of HC3N and C2H2 exhibits characteristics of both pure polymers. This is particularly important as pure polyacetylenes do not match the optical constants measured for Titan's atmospheric hazes. The copolymers produced by the incorporation of other minor atmospheric constituents, like HC3N, into the polyacetylenes are expected to have optical constants more comparable to those of the Titan haze.

Non-NASA Center

Aluminosilicate colloidal gels: from the early age to the precipitation of zeolites

Aluminosilicate hydrogels are often considered to be precursors for the crystallisation of zeolites carried out under hydrothermal conditions. The preparation of mechanically homogeneous aluminosilicate gels enables the study of these materials through bulk rheology and observation of the aging dynamics until the precipitation of crystalline zeolites. The first part of this study deals with the establishment of ternary state diagrams, in order to identify the range of chemical formulations that enable preparation of single-phase homogeneous gels. Then, by studying the viscoelastic moduli during the gelation reaction, and by yielding the gel under large deformation, we propose an empirical law considering the partial order of reaction on each chemical element, to predict the gelation time according to the chemical formulation. The scaling behavior of the elastic properties of this colloidal gel shows a transition from a strong link behavior to a weak link regime. Long term aging results in the shrinkage of the gel, accompanied by syneresis of interstitial liquid at the surface. Zeolites precipitate through crystallisation by a particle attachment mechanism, when thermodynamic equilibrium is reached. The stoichiometry of the precipitated zeolites is not only consistent with the concentration of the remaining species in the supernatant but, surprisingly, it is also very close to the partial order of the reaction of the chemical elements involved in the determination of the critical gel point. This indicates a strong correlation between the morphology of the soft amorphous gel network that is formed at an early age and those of the final solid precipitated crystals.

36 MATERIALS SCIENCE

Raman properties of various carbonaceous materials and their astrophysical implications

It is well known that a large number of celestial objects exhibit, in the range 3 to 12 micron, a family of emission features called unidentified infrared bands (UIR). They usually appear together and are associated with UV sources. Recently various authors have suggested that these features could be attributed to solid carbonaceous materials. Following this interest, a systematic analysis was performed of various types of amorphous carbon grains and polycyclic aromatic hydrocarbons (PAH), produced in lab. Updating results of Raman measurements performed on several carbonaceous materials, chosen according to their astrophysical interest, are presented. The measurements were made by means of a Jobin-Yvon monochromator HG2S and standard DC electronic. The line at 5145 A of an Ar+ laser was used as excitation source.

Blanco, A.

Visualizing the impact of quenched disorder on 2D electron Wigner solids

Electron Wigner solids (WSs) provide an ideal system for understanding the competing effects of electron–electron and electron–disorder interactions, a central unsolved problem in condensed matter physics. Progress in this topic has been limited by a lack of single-defect-resolved experimental measurements as well as accurate theoretical tools to enable realistic experiment/theory comparison. Here, in this study, we overcome these limitations by combining atomically resolved scanning tunnelling microscopy (STM) with neural-quantum-state quantum Monte Carlo (NQS-QMC) simulation of disordered 2D electron WSs to discover new disorder-induced physical regimes of correlated electron behaviour. STM was used to image the electron density (n e )-dependent evolution of electron WSs in gate-tunable bilayer MoSe 2 (BL-MoSe 2 ) devices with varying long-range (n LR ) and short-range (n SR ) disorder densities. These images were compared with NQS-QMC simulations using realistic disorder maps extracted from experiment, thus allowing the roles of different disorder types to be disentangled. We identify two distinct physical regimes for disordered electron WSs that depend on n SR . For n SR ≲ n e , the WS behaviour is dominated by long-range disorder and features extensive mixed solid–liquid phases, a new type of local re-entrant melting/crystallization and prominent Friedel oscillations. By contrast, when n SR ≫ n e , these features are suppressed and a more robust amorphous WS phase emerges that persists to higher n e , highlighting the importance of short-range disorder in this regime. Our work establishes a powerful framework for studying disordered quantum solids through a combined experimental–theoretical approach.

Ge, Zhehao [University of California, Berkeley, CA

Optical constants of solid methane

Methane is the most abundant simple organic molecule in the outer solar system bodies. In addition to being a gaseous constituent of the atmospheres of the Jovian planets and Titan, it is present in the solid form as a constituent of icy surfaces such as those of Triton and Pluto, and as cloud condensate in the atmospheres of Titan, Uranus, and Neptune. It is expected in the liquid form as a constituent of the ocean of Titan. Cometary ices also contain solid methane. The optical constants for both solid and liquid phases of CH4 for a wide temperature range are needed for radiative transfer calculations, for studies of reflection from surfaces, and for modeling of emission in the far infrared and microwave regions. The astronomically important visual to near infrared measurements of solid methane optical constants are conspicuously absent from the literature. Preliminary results are presented on the optical constants of solid methane for the 0.4 to 2.6 micrometer region. Deposition onto a substrate at 10 K produces glassy (semi-amorphous) material. Annealing this material at approximately 33 K for approximately 1 hour results in a crystalline material as seen by sharper, more structured bands and negligible background extinction due to scattering. The constant k is reported for both the amorphous and the crystalline (annealed) states. Typical values (at absorption maxima) are in the .001 to .0001 range. Below lambda = 1.1 micrometers the bands are too weak to be detected by transmission through the films less than or equal to 215 micrometers in thickness, employed in the studies to date. Using previously measured values of the real part of the refractive index, n, of liquid methane at 110 K, n is computed for solid methane using the Lorentz-Lorenz relationship. Work is in progress to extend the measurements of optical constants n and k for liquid and solid to both shorter and longer wavelengths, eventually providing a complete optical constants database for condensed CH4.

Khare, Bishun N.

Multi-material additive manufacturing of aluminum 6061-T6 alloy with stainless steel 304: Suppression of intermetallic compounds and interface growth mechanism

Fabricating integrated aluminum-steel structures is difficult because of metallurgical incompatibilities that promote intermetallic compound (IMC) formation at their interfaces. This work introduces a practical route for additively manufacturing 6061-T6 aluminum alloy (AA6061-T6) directly onto 304 stainless steel (SS304) using a high shear strain rate-assisted interfacial bonding mechanism. Through the friction extrusion deposition-based additive manufacturing method, both single- and multi-layer deposits of AA6061-T6 were successfully fabricated on SS304, yielding a robust hybrid multi-material structure. Comprehensive analyses of deposition quality, interface porosity, and bonding performance showed that the interface achieved a tensile strength exceeding 154 MPa under quasi-static loading. Microstructural observations revealed that the deposited aluminum layers experienced severe plastic deformation, resulting in pronounced grain refinement. Importantly, the interfacial zone was found to be free of brittle IMCs, instead containing a thin amorphous layer that evolved through a non-linear reaction-zone growth law. This solid-state additive strategy establishes a promising pathway for lightweight structural systems, nuclear energy component cladding, and multifunctional engineering components, redefining how dissimilar metals can be integrated for advanced applications.

Aluminum alloy

Fast ionic conduction achieved through the design and synthesis of ceramic heterointerfaces

Lithium (Li) chloride and iron oxychloride (FeOCl), typically nonconductive, were combined to form a [Li 1+δ Cl] δ+ /[FeOCl] δ- heterointerface composite material (LFH), achieving ionic conductivities of >1 mS cm -1 . Analysis techniques (scanning transmission electron microscopy [STEM] and electron energy-loss spectroscopy [EELS]) indicated that the microstructure of LFH consisted of an amorphous LiCl-based shell surrounding a crystalline FeOCl-based core. Electrochemical measurements alongside solid-state 6,7 Li nuclear magnetic resonance (NMR) and molecular dynamic simulations revealed Li+ as the sole conductive species, with a diffusion barrier of ~0.25 eV. X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) results further supported interstitial Li + diffusion at the heterointerface and within the LiCl phase, made possible by the heterointerface. Despite susceptibility to electronic conductivity, iron’s defects and multivalency (Fe³⁺, Fe²⁺) enable the Fe–O–Cl framework to accept Cl - , facilitating Li⁺ ionic conduction. Finally, a prototype solid-state cell (showing 97% Coulombic efficiency) demonstrated the viability of this heterointerface design for applications in energy storage.

36 MATERIALS SCIENCE