Mechanistic understanding of speciated oxide growth in high entropy alloys.

Complex multi-element alloys are gaining prominence for structural applications, supplementing steels, and superalloys. Understanding the impact of each element on alloy surfaces due to oxidation is vital in maintaining material integrity. This study investigates oxidation mechanisms in these alloys using a model five-element equiatomic CoCrFeNiMn alloy, in a controlled oxygen environment. The oxidation-induced surface changes correlate with each element's interactive tendencies with the environment, guided by thermodynamics. Initial oxidation stages follow atomic size and redox potential, with the latter becoming dominant over time, causing composition inversion. The study employs in-situ atom probe tomography, transmission electron microscopy, and X-ray absorption near-edge structure techniques to elucidate the oxidation process and surface oxide structure evolution. Our findings deconvolute the mechanism for compositional and structural changes in the oxide film and will pave the way for a predictive design of complex alloys with improved resistance to oxidation under extreme conditions.

Stereo-Structural Fine Tuning of Chromaticity.

Lanthanoid carboxylates were synthesized and in situ self-assembled to illustrate temperature-driven evolution in chromaticity. Evolution in structure (crystallinity), composition, luminosity, and chromaticity were investigated revealing the coupled role of divergence in order/structure (spatial organization), and composition in tuning observed color. Loss of crystallinity or increase in residual carbon leads to decrease in luminosity even with increase in hue. Comparing Ho and Er congeners shows that the density of accessible transition states relates to shifts in low and high wavelength components of color. This work demonstrates that, just as interface dipoles can lead to change in semiconductor band gap, structure and composition can analogously alter observed color.

Predicting Emergence of Nanoscale Order in Surface Oxides through Preferential Interactivity Parameter.

Diffusion and surface oxidation are critical processes in metal alloy designs and use. Surface oxides provide opportunities to improve material properties or performance beyond bulk alterations. Surface oxidation is, however, often oversimplified into a classical diffusion process. Passivating oxide surfaces are also thought to be lacking in complexity or critical information. A closer look, however, shows inherent complexity with kinetics-driven competition between the elements in the process leading to redox-speciation across a very small (nm) thickness. Questions that remain to be answered for a comprehensive understanding of surface oxides are diverse and call for interdisciplinary approaches. By using the thermodynamics-based Preferential Interactivity Parameter (PIP) alongside kinetic consideration, we show how complexity in these oxides can be predicted allowing us to tailor these thin films. We use our work, and that of others, to illustrate predictability while also highlighting that there is still much more to be done.

Atomic Reconstruction of Au Thin Films through Interfacial Strains.

Interfaces play a critical thermodynamic role in the existence of multilayer systems. Due to their utility in bridging energetic and compositional differences between distinct species, the formation of interfaces inherently creates internal strain in the bulk due to the reorganization needed to accommodate such a change. We report the effect of scaling interfacial stress by deposition of different adlayers on a host thin metal film. Intrinsic property differences between host and deposited metal atoms result in varying degree of composition and energy gradient within the interface. Interfacial stress can increase defects in the host leading to (i) energy dissipation and reorganization to minimize surface energy, and (ii) increased material strength. We infer that dissipation of interfacial stress induces defect migration, hence bulk and surface atomic reconstruction as captured by the surface roughness and grain size reduction coupled with a concomitant increase in material strength.

Photo-Activated Growth and Metastable Phase Transition in Metallic Solid Solutions.

Laser processing in metals is versatile yet limited by its reliance on phase transformation through heating rather than electronic excitation due to their low absorptivity, attributing from highly ordered structures. Metastable states (i.e., surfaces, glasses, undercooled liquids), however, present a unique platform, both energetically and structurally to enable energy landscape tuning through selective stimuli. Herein, this ansatz is demonstrated by exploiting thin passivating oxides to stabilize an undercooled state, followed by photo-perturbation of the near surface order to induce convective Marangoni flows, edge-coalescence and phase transition into a larger metastable solid bearing asymmetric composition between the near surface and core of the formed structure. The self-terminating nature of the process creates a perfectly contained system which can maintain a high relaxation energy barrier hence deep metastable states for extended periods of time.

Spatially Directed Pyrolysis via Thermally Morphing Surface Adducts.

Combustion is often difficult to spatially direct or tune associated kinetics-hence a run-away reaction. Coupling pyrolytic chemical transformation to mass transport and reaction rates (Damköhler number), however, we spatially directed ignition with concomitant switch from combustion to pyrolysis (low oxidant). A 'surface-then-core' order in ignition, with concomitant change in burning rate,is therefore established. Herein, alkysilanes grafted onto cellulose fibers are pyrolyzed into non-flammable SiO2 terminating surface ignition propagation, hence stalling flame propagating. Sustaining high temperatures, however, triggers ignition in the bulk of the fibers but under restricted gas flow (oxidant and/or waste) hence significantly low rate of ignition propagation and pyrolysis compared to open flame (Liñán's equation). This leads to inside-out thermal degradation and, with felicitous choice of conditions, formation of graphitic tubes. Given the temperature dependence, imbibing fibers with an exothermically oxidizing synthon (MnCl2 ) or a heat sink (KCl) abets or inhibits pyrolysis leading to tuneable wall thickness. We apply this approach to create magnetic, paramagnetic, or oxide containing carbon fibers. Given the surface sensitivity, we illustrate fabrication of nm- and µm-diameter tubes from appropriately sized fibers.

Role of Nanoscale Roughness and Polarity in Odd-Even Effect of Self-Assembled Monolayers.

The dependency of substrate roughness on wetting properties of self-assembled monolayers (SAMs) has been studied extensively, but most previous studies used limited selection of probing liquid and range of surface roughness. These studies disregarded the limit to observation of sub-nanometer odd-even parity effect, hence are inconclusive. In this work we report the role of solvent polarity on the roughness-dependency of wetting behavior of SAMs by studying static con-tact angle of a variety of probing liquids, with different polarities, on SAMs formed on Ag-based substrate with different surface morphology. By overlapping the roughness ranges with previous studies on Au, the limitation of surface roughness (RMS=1 nm) to observation of the odd-even effect using water as probing liquid was confirmed, but other probing liquid yielded different roughness-dependent behaviors, with more polar solvent showing more roughness-dependent behavior. Based on these observations, we concluded that there exists a phase-transition like behavior in SAMs due to substrate roughness and molecule chain length, but whose determination is dependent on the probing liquid.

Passivation-driven speciation, dealloying and purification.

Thin passivating surface oxide layers on metal alloys form a dissipation horizon between dissimilar phases, hence harbour an inherent free energy and composition gradient. We exploit this gradient to drive order and selective surface separation (speciation), enabling redox-driven enrichment of the core by selective conversion of low standard reduction potential (E°) components into oxides. Coupling this oxide growth to volumetric changes during solidification allows us to create oxide crystallites trapped in a metal ('ship-in-a-bottle') or extrusion of metal fingerlings on the heavily oxidized particle. We confirm the underlying mechanism through high temperature X-ray diffraction and characterization of solidification-trapped particle states. We demonstrate that engineering the passivating surface oxide can lead to purification via selective dealloying with concomitant enrichment of the core, leading to disparate particle morphologies.

Molecular Conformation in Charge Tunneling across Large-Area Junctions.

Self-assembled monolayers are predicated on thermodynamic equilibrium; hence, their properties project accessible relaxation pathways. Herein, we demonstrate that charge tunneling correlates with conformational degrees of freedom(s). Results from open chain and cyclic head groups show that, as expected, distribution in tunneling data correlates with the orientation of the head group, akin to the odd-even effect and more importantly the degree of conformational freedom, but fluctuates with applied bias. Trends in nature of distributions in current density illuminate the need for higher statistical moments in understanding these rather dynamic systems. We employ skewness, kurtosis, and estimation plots to show that the conformational degree of freedom in the head group significantly amplifies the odd-even effect and may lead to enhanced or perturbed tunneling based on whether the head group is on an odd- or even-parity spacer.

Tunable Hydrophobicity via Dimensionally Confined Polymerization of Organometallic Adducts.

Fabrication of tunable fine textures on solid metal surfaces often demands sophisticated reaction/processing systems. By exploiting in situ polymerization and self-assembly of inorganic adducts derived from liquid metals (the so-called HetMet reaction) with concomitant solidification, solid metal films with tunable texture are readily fabricated. Serving as a natural dimensional confinement, interparticle pores and capillary-adhered thin liquid films in a pre-packed bed of undercooled liquid metal particles lead to the expeditious surface accumulation of organometallic synthons, which readily oligomerize and self-assemble into concentration-dictated morphologies/patterns. Tuning particle size, particle packing (flat or textured), and reactant concentration generates diverse, autonomously organized organometallic structures on a metal particle bed. Concomitant solidification and sintering of the underlying undercooled particle bed led to a multiscale patterned solid metal surface. The process is illustrated by creating tunable features on pre-organized metal particle beds with concomitant tunable wettability as illustrated through the so-called petal and lotus effects.

Biobased superhydrophobic coating enabled by nanoparticle assembly.

Understanding biobased nanocomposites is critical in fabricating high performing sustainable materials. In this study, fundamental nanoparticle assembly structures at the nanoscale are examined and correlated with the macroscale properties of coatings formulated with these structures. Nanoparticle assembly mechanisms within biobased polymer matrices were probed using in situ liquid-phase atomic force microscopy (AFM) and computational simulation. Furthermore, coatings formulated using these nanoparticle assemblies with biobased polymers were evaluated with regard to the hydrophobicity and adhesion after water immersion. Two biobased glycopolymers, hydroxyethyl cellulose (HEC) and hydroxyethyl starch (HES), were investigated. Their repeating units share the same chemical composition and only differ in monomer conformations (α- and ß-anomeric glycosides). Unique fractal structures of silica nanoparticle assemblies were observed with HEC, while compact clusters were observed with HES. Simulation and AFM measurement suggest that strong attraction between silica surfaces in the HEC matrix induces diffusion-limited-aggregation, leading to large-scale, fractal assembly structures. By contrast, weak attraction in HES only produces reaction-limited-aggregation and small compact cluster structures. With high particle loading, the fractal structures in HEC formed a network, which enabled a waterborne formulation of superhydrophobic coating after silane treatment. The silica nanoparticle assembly in HEC was demonstrated to significantly improve adhesion, which showed minimum adhesion loss even after extended water immersion. The superior performance was only observed with HEC, not HES. The results bridge the assembly structures at the nanoscale, influenced by molecular conformation of biobased polymers, to the coating performance at the macroscopic level. Through this study we unveil new opportunities in economical and sustainable development of high-performance biobased materials.

Stabilization of Undercooled Metals via Passivating Oxide Layers.

Undercooling metals relies on frustration of liquid-solid transition mainly by an increase in activation energy. Passivating oxide layers are a way to isolate the core from heterogenous nucleants (physical barrier) while also raising the activation energy (thermodynamic/kinetic barrier) needed for solidification. The latter is due to composition gradients (speciation) that establishes a sharp chemical potential gradient across the thin (0.7-5 nm) oxide shell, slowing homogeneous nucleation. When this speciation is properly tuned, the oxide layer presents a previously unaccounted for interfacial tension in the overall energy landscape of the relaxing material. We demonstrate that 1) the integrity of the passivation oxide is critical in stabilizing undercooled particle, a key tenet in developing heat-free solders, 2) inductive effects play a critical role in undercooling, and 3) the magnitude of the influence of the passivating oxide can be larger than size effects in undercooling.

Heat-Free Biomimetic Metal Molding on Soft Substrates.

Fabrication of bio-templated metallic structures is limited by differences in properties, processing conditions, packing, and material state(s). Herein, by using undercooled metal particles, differences in modulus and processing temperatures can be overcome. Adoption of autonomous processes such as self-filtration, capillary pressure, and evaporative concentration leads to enhanced packing, stabilization (jamming) and point sintering with phase change to create solid metal replicas of complex bio-based features. Differentiation of subtle differences between cultivars of the rose flower with reproduction over large areas shows that this biomimetic metal patterning (BIOMAP) is a versatile method to replicate biological features either as positive or negative reliefs irrespective of the substrate. Using rose petal patterns, we illustrate the versatility of bio-templated mapping with undercooled metal particles at ambient conditions, and with unprecedented efficiency for metal structures.

Chameleon Metals: Autonomous Nano-Texturing and Composition Inversion on Liquid Metals Surfaces.

Studies on passivating oxides on liquid metals are challenging, in part, due to plasticity, entropic, and technological limitations. In alloys, compositional complexity in the passivating oxide(s) and underlying metal interface exacerbates these challenges. This nanoscale complexity, however, offers an opportunity to engineer the surface of the liquid metal under felicitous choice of processing conditions. We inferred that difference in reactivity, coupled with inherent interface ordering, presages exploitable order and selectivity to autonomously present compositionally biased oxides on the surface of these metals. Besides compositional differences, sequential release of biased (enriched) components, via fractal-like paths, allows for patterned layered surface structures. We, therefore, present a simple thermal-oxidative compositional inversion (TOCI) method to introduce fractal-like structures on the surface of these metals in a controlled (tier, composition, and structure) manner by exploiting underlying stochastic fracturing process. Using a ternary alloy, a three-tiered (in structure and composition) surface structure is demonstrated.

Determining Surface Energy of Porous Substrates by Spray Ionization.

We have developed a new spray-based method for characterizing surface energies of planar, porous substrates. Distinct spray modes (electrospray versus electrostatic spray), from the porous substrates, occur in the presence of an applied DC potential after wetting with solvents of different surface tension. The ion current resulting from the spray process is maximized when the surface energy of the porous substrate approaches the surface tension of the wetting solvent. By monitoring the selected ion current (e.g., benzoylecgonine, m/z 290 → 168) with a mass spectrometer or the total ion current with an ammeter, we determined the solvent surface tension yielding the maximum ion current to indicate the surface energy of the solid. Detailed evaluations using polymeric substrates of known surface energies enabled effective calibration of the approach that resulted in the correct estimation of the surface energy of hydrophobic paper substrates prepared by gas-phase silanization. A three-parameter empirical model suggests that the experimentally observed ion current profile is governed by differential partitioning of analyte controlled by the interfacial forces between the wetting solvent and the porous substrate.

Ambient synthesis of nanomaterials by in situ heterogeneous metal/ligand reactions.

Coordination polymers are ideal synthons in creating high aspect ratio nanostructures, however, conventional synthetic methods are often restricted to batch-wise and costly processes. Herein, we demonstrate a non-traditional, frugal approach to synthesize 1D coordination polymers by in situ etching of zerovalent metal particle precursors. This procedure is denoted as the heterogeneous metal/ligand reaction and was demonstrated on Group 13 metals as a proof of concept. Simple carboxylic acids supply the etchant protons and ligands for metal ions (conjugate base) in a 1 : 1 ratio. This scalable reaction produces a 1D polymer that assembles into high-aspect ratio 'nanobeams'. We demonstrate control over crystal structure and morphology by tuning the: (i) metal center, (ii) stoichiometry and (iii) structure of the ligands. This work presents a general scalable method for continuous, heat free and water-based coordination polymer synthesis.

Inverting Thermal Degradation ( iTD) of Paper Using Chemi- and Physi-Sorbed Modifiers for Templated Material Synthesis.

Fibrous cellulosic materials have been used as templates for material synthesis or organization via thermal degradation of the cellulose. Most of these methods, however, fail to exploit fiber organization, in part due to loss of structure with processing. Herein, we demonstrate that chemi- and physi-sorbed modifiers of cellulose alters the thermal degradation mechanism allowing for controlled deposition of oxide and carbon (incomplete combustion) along the original paper fiber network. We demonstrate that the degradation of the cellulose fibers depends on the amount of physisorbed material due, in part, to effect on the propagation of the ignition event. From the distribution of the residual elements and shape of the deposits, we can infer that the thermal degradation process depends on the nature, and concentration, of filler(s) or occluded.

Elucidating the Role of Molecule-Electrode Interfacial Defects in Charge Tunneling Characteristics of Large-Area Junctions.

Interfacial chemistry at organic-inorganic contact critically determines the function of a wide range of molecular and organic electronic devices and other systems. The chemistry is, however, difficult to understand due to the lack of easily accessible in-operando spectroscopic techniques that permit access to interfacial structure on a molecular scale. Herein, we compare two analogous junctions formed with identical organic thin film and different liquid top-contacts (water droplet vs eutectic gallium indium alloy) and elucidate the puzzling interfacial characteristics. Specifically, we fine-tune the surface topography of the organic surface using mixed self-assembled monolayers (SAMs): single component SAM composed of rectifier (2,2'-bipyridyl-terminated n-undecanethiolate; denoted as SC11BIPY) is systematically diluted with nonrectifying n-alkanethiolates of different lengths (denoted as SC n where n = 8, 10, 12, 14, 16, 18). Characterization of the resulting mixed SAMs in wettability and tunneling currents with the two separate liquid top-contacts allows us to investigate the role of phase segregation and gauche defect in the SAM//liquid interfaces. The results reported here show the difference in length between SC11BIPY and SC n is translated into nanoscopic pits and gauche-conformer defects on the surface, and the difference in contact force-hydrostatic vs user pressures-and hence conformity of contact account for the difference in wettability and rectification behaviors. Our work provides an insight into the role of molecule-electrode interfacial defects in performance of molecular-scale electronic devices.

Understanding Keesom Interactions in Monolayer-Based Large-Area Tunneling Junctions.

Charge transport across self-assembled monolayers (SAMs) has been widely studied. Discrepancies of charge tunneling data that arise from various studies, however, call for efforts to develop new statistical analytical approaches to understand charge tunneling across SAMs. Structure-property studies on charge tunneling across SAM-based junctions have largely been through comparison of average tunneling rates and associated variance. These early moments (especially the average) are dominated by barrier width-a static property of the junction. In this work, we show that analysis of higher statistical moments (skewness and kurtosis) reveals the dynamic nature of the tunnel junction. Intramolecular Keesom (dipole-dipole) interactions dynamically fluctuate with bias as dictated by stereoelectronic limitations. Analyzing variance in the distribution of tunneling data instead of the first statistical moment (average), for a series of n-alkanethiols containing internal amide and aromatic terminal groups, we observe that the direction of dipole moments affects molecule-electrode coupling. An applied bias induces changes in the tunneling probability, affecting the distribution of tunneling paths in large-area molecular junctions.

Dried Blood Spheroids for Dry-State Room Temperature Stabilization of Microliter Blood Samples.

It is well-known that 2D dried blood spots on paper offer a facile sample collection, storage, and transportation of blood. However, large volume requirements, possible analyte instability, and difficult sample recovery plague this method, lowering confidence in analyte quantification. For the first time, we demonstrate a new approach using 3D dried blood spheroids for stabilization of small volume blood samples, mitigating these effects without cold storage. Blood spheroids form on hydrophobic paper, preventing interaction between the sample and paper substrate, eliminating all chromatographic effects. Stability of the enzyme alanine transaminase and labile organic compounds such as cocaine and diazepam were also shown to increase in the spheroid by providing a critical radius of insulation. On-surface analysis of the dried blood spheroids using paper spray mass spectrometry resulted in sub-ng/mL limits of detection for all illicit drugs tested, representing 1 order of magnitude improvement compared with analysis from 2D dried blood spots.