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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

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↗
DOE OSTI2023

Substantial lifetime enhancement for Si-based photoanodes enabled by amorphous TiO2 coating with improved stoichiometry

Abstract Amorphous titanium dioxide (TiO 2 ) film coating by atomic layer deposition (ALD) is a promising strategy to extend the photoelectrode lifetime to meet the industrial standard for solar fuel generation. To realize this promise, the essential structure-property relationship that dictates the protection lifetime needs to be uncovered. In this work, we reveal that in addition to the imbedded crystalline phase, the presence of residual chlorine (Cl) ligands is detrimental to the silicon (Si) photoanode lifetime. We further demonstrate that post-ALD in-situ water treatment can effectively decouple the ALD reaction completeness from crystallization. The as-processed TiO 2 film has a much lower residual Cl concentration and thus an improved film stoichiometry, while its uniform amorphous phase is well preserved. As a result, the protected Si photoanode exhibits a substantially improved lifetime to ~600 h at a photocurrent density of more than 30 mA/cm 2 . This study demonstrates a significant advancement toward sustainable hydrogen generation.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Cobalt-free composite-structured cathodes with lithium-stoichiometry control for sustainable lithium-ion batteries

Abstract Lithium-ion batteries play a crucial role in decarbonizing transportation and power grids, but their reliance on high-cost, earth-scarce cobalt in the commonly employed high-energy layered Li(NiMnCo)O 2 cathodes raises supply-chain and sustainability concerns. Despite numerous attempts to address this challenge, eliminating Co from Li(NiMnCo)O 2 remains elusive, as doing so detrimentally affects its layering and cycling stability. Here, we report on the rational stoichiometry control in synthesizing Li-deficient composite-structured LiNi 0.95 Mn 0.05 O 2 , comprising intergrown layered and rocksalt phases, which outperforms traditional layered counterparts. Through multiscale-correlated experimental characterization and computational modeling on the calcination process, we unveil the role of Li-deficiency in suppressing the rocksalt-to-layered phase transformation and crystal growth, leading to small-sized composites with the desired low anisotropic lattice expansion/contraction during charging and discharging. As a consequence, Li-deficient LiNi 0.95 Mn 0.05 O 2 delivers 90% first-cycle Coulombic efficiency, 90% capacity retention, and close-to-zero voltage fade for 100 deep cycles, showing its potential as a Co-free cathode for sustainable Li-ion batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Combinatorial screening of crystal structure in Ba-Sr-Mn-Ce perovskite oxides with ABO 3 stoichiometry

ABO 3 oxides with the perovskite-related structures are attracting significant interest due to their promising physical and chemical properties for many applications requiring tunable chemistry, including fuel cells, catalysis, and electrochemical water splitting. Here we report on the crystal structure of the entire family of perovskite oxides with ABO 3 stoichiometry, where A and B are Ba, Sr, Mn, Ce. Given the vast size of this chemically complex material system, exploration for stable perovskite-related structures with respect to its constituent elements and annealing temperature is performed by combinatorial pulsed laser deposition and spatially-resolved characterization of composition and structure. As a result of this high-throughput experimental study, we identify hexagonal perovskite-related polytypic transformation as a function of composition in the Ba 1-x Sr x MnO 3 oxides after annealing at different temperatures. Furthermore, a hexagonal perovskite-related polytype is observed in a narrow composition-temperature range of the Ba 1-x Sr x MnO 3 oxides. In contrast, a tetragonally-distorted perovskite is observed across a wider range of compositions and annealing temperatures in the Sr 1-x Ce x MnO 3 oxides. This structure stability is further enhanced along the Ba 1-x Sr x MnO 3 - Sr 1-x Ce x MnO 3 pseudo-binary tie-line at x=0.25 by increasing Ba-incorporation and annealing temperature. These results indicate that the BaCe x Mn 1-x O 3 - Sr 1-x Ce x MnO 3 pseudo-binary oxide alloys (solid solutions) with tetragonal perovskite structure and broad composition-temperature range of stability are promising candidates for thermochemical water splitting applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Unusual aliovalent doping effects on oxygen non-stoichiometry in medium-entropy compositionally complex perovskite oxides

Aliovalent doping of perovskite oxides can tune the oxygen vacancy formation energy. This work discovers normal vs. abnormal aliovalent doping effects on redox behaviors in medium-entropy compositionally complex perovskite oxides (CCPOs) (La 1–x Sr x )(Mn 1/3 Fe 1/3 Ti 1/3 )O 3–δ (LS_MFT) vs. (La 1–x Sr x )(Mn 1/3 Fe 1/3 Cr 1/3 )O 3–δ (LS_MFC). In the LS_MFC series, the oxygen non-stoichiometry range Δδ (= δ red – δ ox ) linearly depends on the Sr molar ratio x, while the LS_MFT series shows a V-shape dependence of Δδ on x. This unusual observation is investigated and explained based on the analysis of the energy loss near edge structure (ELNES) in STEM electron energy loss spectroscopy, along with density functional theory (DFT) calculations. In LS_MFC, Cr–L 2,3 , Mn–L 2,3 and Fe–L 2,3 peaks have a similar linear shift to higher energy with increasing x, which indicates higher oxidation states of Cr, Mn, and Fe with lower oxygen vacancy formation energies. In LS_MFT, the V-shape of the Δδ vs. x curve is caused by the stable Ti 4+ state and a V-shape Mn/Fe valency dependence on x. Furthermore, this study suggests the possible existence of different (including unexpected) coupled aliovalent doping effects in CCPOs with multiple B-site redox active elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Hydrogen in disordered titania: connecting local chemistry, structure, and stoichiometry through accelerated exploration

Hydrogen incorporation in native surface oxides of metal alloys often controls the onset of metal hydriding, with implications for materials corrosion and hydrogen storage. A key representative example is titania, which forms as a passivating layer on a variety of titanium alloys for structural and functional applications. These oxides tend to be structurally diverse, featuring polymorphic phases, grain boundaries, and amorphous regions that generate a disparate set of unique local environments for hydrogen. Here, we introduce a workflow that can efficiently and accurately navigate this complexity. First, a machine learning force field, trained on ab initio molecular dynamics simulations, was used to generate amorphous configurations. Density functional theory calculations were then performed on these structures to identify local oxygen environments, which were compared against experimental observations. Second, to classify subtle differences across the disordered configuration space, we employ a graph-based sampling procedure. Finally, local hydrogen binding energies and hopping kinetics are computed using exhaustive density functional theory calculations on representative configurations. Here, we leverage this methodology to show that hydrogen binding energetics are described by local oxygen coordination, which in turn is affected by stoichiometry, and form the basis of hopping kinetics and diffusion. Together these results imply that hydrogen incorporation and transport in TiO x can be tailored through compositional engineering, with implications for improving the performance and durability of titanium-derived alloys in hydrogen environments.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Electrochemical control over stoichiometry via cation intercalation into Chevrel-phase sulphides (Cu x Mo 6 S 8 , x = 1-3)

Herein this work presents a systematic investigation of the electrochemical intercalation of aqueous copper cations into the Chevrel phase (CP) Mo 6 S 8 and its effect on the host's electronic and structural characteristics as a function of stoichiometry. The electrochemical potentials at which copper intercalates into the CP Mo 6 S 8 host in 1 M CuSO 4 were identified for Cu x Mo 6 S 8 (x = 1–3) as 0.23 V, 0.11 V, and 0.055 V (vs. Cu/Cu 2+ ) for Cu 1 Mo 6 S 8 , Cu 2 Mo 6 S 8 , and Cu 3 Mo 6 S 8 , respectively, and correlated via ex situ PXRD to stoichiometric content. Potentials were also identified that yield non-stoichiometric phases with traceable Cu content-dependent structural changes. Ab initio DFT calculations were performed to probe thermodynamic stability of Cu x Mo 6 S 8 CP compositions and the metal-to-semiconductor transitions as a function of copper content. Lastly, we demonstrate that the SK-pre-edge intensity is a successful probe for intercalant content: as copper equivalents increase, so does charge transfer to the partially occupied S 3p orbitals, resulting in a decrease in the pre-edge intensity corresponding to the excitation of a S 1s-to-3p/Mo 4d hybridized orbital.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Effects of stoichiometry and epitaxial strain on the stabilization of infinite-layer nickelates

The discovery of superconductivity in infinite-layer nickelates has sparked great interest due to their potential analogy with the unconventional cuprate superconductors. However, investigations of this system have been limited by the challenges in materials control and synthesis driven by substantial thermodynamic instability, making it difficult to reach an experimental consensus. Hence, establishing a robust synthetic route to highly crystalline infinite-layer nickelates is of paramount importance. Here, we present and discuss recent progress on the reproducible two-step synthesis of (Nd,Sr)NiO2 via the stabilization of high-quality perovskite nickelates and the subsequent topotactic transition to the infinite-layer phase. In particular, we discuss the important factors, such as cation stoichiometry and epitaxial strain, which significantly impact the crystallinity of both phases, accompanied by careful structural characterization. These results on robust synthesis can help accelerate the experimental investigation of the intrinsic physical properties of these complex strongly correlated materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Water chemistry in flume channel and hyporheic zone (i.e., porewater) associated with: “Rethinking Aerobic Respiration in the Hyporheic Zone Under Variation in Carbon and Nitrogen Stoichiometry”

Dissolved oxygen (DO), total organic carbon (TOC), total nitrogen (TN), molecular data for organic matter, and biochemical reactions for surface water and porewater (i.e., hyporheic zone) collected from a water recirculating flume located at the University of Texas, Austin. The flume contained real river water from Lower Colorado River(Austin, TX) and clean sand. Hyporheic exchange in the flume was induced through The study aims to understand relationships between aerobic metabolism of organic matter and molecular characteristics of organic matter, such as thermodynamic signature and nitrogen content, through the extent of the hyporheic zone at 10 cm- resolution, and through time. During the experiment, organic matter (dry leaves) was added to the flume and removed after 24 hours. The water samples were collected before the addition of leaves, at the time of removal of leaves, and at hour 72. The water samples were analyzed using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and total organic carbon (TOC) and total nitrogen (TN) analysis. Dissolved oxygen content throughout the surface water and the hyporheic zone of the flume was measured with a large planar optode. This data package is associated with the publication ’ Rethinking Aerobic Respiration in the Hyporheic Zone Under Variation in Carbon and Nitrogen Stoichiometry’ published in Environmental Science and Technology (Turețcaia et al., 2023 https://doi.org/10.1021/acs.est.3c04765). The dataset is comprised of five folders (1) Diss_O2_pic, (2) input_files (3) output_files; (4) python_code; and (5) R_code . Diss_O2_pic contains siximages of dissolved oxygen distribution in a bedform at hours 0, 24, and 72 of the experiment conducted in a large recirculation flume. Images are in separate R and G channels (i.e., RGB). The input_files contains (1) a csv file with FTICR peaks identified within each sample, (2) a csv file with molecular information pertinent to FTICR data with Gibbs free energy calculations adjusted for environmental temperature, (3) a csv file containing concentrations of non-purgeable organic carbon measured throughout the experiment , (4) a csv file containing concentrations of total nitrogen measured throughout the experiment, (5) a csv file containing total biochemical reactions (i.e., transformations) identified in the dataset, (6) a csv containing transformation profiles, and (7) a csv file containing transformations with formulas, and (8) a jpg file with schematic representation of locations for sample collection. The output_files contains (1) and xlsx file containing percent biochemical reactions containing nitrogen identified across all 39 sample, (2) a csv file of merged FTICR data and molecular information files, (3) a csv files containing average Gibbs free energy within sampling domains and at each sampling location, (4) a csv file with average concentrations of dissolved oxygen across sampling locations at hour 0, (5) a csv file with average concentrations of dissolved oxygen across sampling locations at hour 24, (6) a csv file with average concentrations of dissolved oxygen across sampling locations at hour 72, (7) a csv file with percent chemical classes identified across sampling locations at hour 0, (8) a csv file with percent chemical classes identified across sampling locations at hour 24, (9) a csv file with percent chemical classes identified across sampling locations at hour 72, and (10) a csv file containing percent nitrogen containing biochemical reactions identified across sampling locations at hours 0, 24, and 72. The python_code contains seven ipynb files which are Jupyter Notebooks used for data analysis and figures generation. The R_code contains 3 R files with R code used for data analysis and figures generation. This data package contains the processed data used in the associated manuscript. This data has not been previously published.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

N and P constrain C in ecosystems under climate change: Role of nutrient redistribution, accumulation, and stoichiometry

Abstract We use the Multiple Element Limitation (MEL) model to examine responses of 12 ecosystems to elevated carbon dioxide (CO 2 ), warming, and 20% decreases or increases in precipitation. Ecosystems respond synergistically to elevated CO 2 , warming, and decreased precipitation combined because higher water‐use efficiency with elevated CO 2 and higher fertility with warming compensate for responses to drought. Response to elevated CO 2 , warming, and increased precipitation combined is additive. We analyze changes in ecosystem carbon (C) based on four nitrogen (N) and four phosphorus (P) attribution factors: (1) changes in total ecosystem N and P, (2) changes in N and P distribution between vegetation and soil, (3) changes in vegetation C:N and C:P ratios, and (4) changes in soil C:N and C:P ratios. In the combined CO 2 and climate change simulations, all ecosystems gain C. The contributions of these four attribution factors to changes in ecosystem C storage varies among ecosystems because of differences in the initial distributions of N and P between vegetation and soil and the openness of the ecosystem N and P cycles. The net transfer of N and P from soil to vegetation dominates the C response of forests. For tundra and grasslands, the C gain is also associated with increased soil C:N and C:P. In ecosystems with symbiotic N fixation, C gains resulted from N accumulation. Because of differences in N versus P cycle openness and the distribution of organic matter between vegetation and soil, changes in the N and P attribution factors do not always parallel one another. Differences among ecosystems in C‐nutrient interactions and the amount of woody biomass interact to shape ecosystem C sequestration under simulated global change. We suggest that future studies quantify the openness of the N and P cycles and changes in the distribution of C, N, and P among ecosystem components, which currently limit understanding of nutrient effects on C sequestration and responses to elevated CO 2 and climate change.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Tuning Stoichiometry to Promote Formation of Binary Colloidal Superlattices

The self-assembly of binary nanoparticle superlattices from colloidal mixtures is a promising method for the fabrication of complex colloidal cocrystal structures. However, binary mixtures often form amorphous or metastable phases instead of the thermodynamically stable phase. Here we show that in binary mixtures of differently sized spherical particles, an excess of the smaller component can promote—and, in some cases, may be necessary for—the self-assembly of a binary cocrystal. Using computer simulations, we identify two mechanisms responsible for this phenomenon. First, excess small particles act like plasticizers and enable systems to reach a greater supersaturation before kinetic arrest occurs. Second, they can disfavor competing structures that may interfere with the growth of the target structure. We find the phase behavior of simulated mixtures of nearly hard spheres closely matches published experimental results. We demonstrate the generality of our findings for mixtures of particles of arbitrary shape by presenting a binary mixture of hard shapes that only self-assembles with an excess of the smaller component.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Sr 2 Fe 2–X Mo X O 6 double perovskites as electrocatalysts for oxidative dehydrogenation of ethane: Effect of B-site stoichiometry

The oxidative dehydrogenation of ethane (ODHE) was investigated using a solid oxide electrocatalytic cell with Sr 2 Fe 2–X Mo X O 6–δ (SFM) double perovskite as the anode electrocatalyst. As shown in the XRD patterns, SFM perovskites maintained their cubic structure upon modifying the B-site ratios of Mo and Fe. Increasing the Mo content of the perovskite structure resulted in a lower water signal intensity at low temperatures in TPR profiles, indicative of moderate oxygen transport through the perovskite structure. Because Mo–O bonds are stronger than Fe–O bonds, the electrical conductivity of SFM perovskites decreased with increasing Mo content. When operated at 100 mA cm –2 , ODHE activity improved four times compared to open circuit voltage, resulting in 16.1% conversion of C 2 H 6 and 83.1% selectivity to C 2 H 4 . It has been demonstrated that oxygen ions provided by perovskite lattices were the key species involved in activating C 2 H 6 based on the in-situ DRIFTS experiments. In conclusion, the SFM perovskite with higher Mo content showed the highest conversion and selectivity due moderate oxygen ion mobility and fast desorption of C 2 H 4 .

25 ENERGY STORAGE↗
DOE OSTI2022

The formation and evolution of Ni 2 Cr precipitates in Ni–Cr model alloys as a function of stoichiometry characterized by synchrotron x-ray diffraction

Ni-based alloys containing significant amounts of Cr, may precipitate new phases during long-term service at elevated temperatures. In Ni–Cr model alloys, the formation of Ni 2 Cr has been found to impact the material properties, including the strength and ductility after isothermal aging below the critical temperature of 590°C. In this work, we quantify the formation and evolution of long-range ordering in four Ni–Cr binary model alloys (Ni/Cr = 1.8, 2.0, 2.2, 2.4) after isothermal aging up to 10,000h at temperatures between 373 and 475°C. The alloys were characterized by hardness testing and synchrotron-based x-ray diffraction to quantify the impact of Ni 2 Cr phase fraction and precipitate size on mechanical properties. After 500h of isothermal aging, the formation of Ni 2 Cr was detected in all four alloys at 475°C. In the stochiometric alloy samples (Ni/Cr = 2.0), the formation of Ni 2 Cr was found after 500 and 3000h aging at 418 and 373°C, respectively. We found that the matrix lattice contraction and Ni 2 Cr phase fraction both saturate after early aging times. This is in stark contrast to the hardness and Ni 2 Cr precipitate size that both continue to increase with increasing aging time. Our results highlight that changes in hardness correlate linearly with Ni 2 Cr precipitate size rather than phase fraction. This important structure-property relationship can potentially help define Ni–Cr-based component lifetimes directly through an understanding of how Ni 2 Cr formation impacts strength and ductility. Here, we find that a precipitation hardening model for critical resolved shear stress with weakly coupled dislocations shows good agreement with the material property changes quantified from experimental measurements.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Anhydrous vs Hydrated f-Element Acetate Polymers Dictated by the Stoichiometry of Protic Acidic/Basic Azole Mixtures

Continuing our investigations of ionic liquid (IL) based routes to a library of f-element/soft donor complexes which could be studied crystallographically, we have explored the dissolution of f-element salts in protic imidazole-based ILs containing only soft donors at high temperatures to drive off volatiles, including water and carboxylic or mineral acids. Here we present our results, reacting acidic and basic azoles in 1:3 or 1:1 stoichiometric compositions at elevated temperature, followed by saturation with Nd(OAc) 3 ·xH 2 O or Ce(OAc) 3 ·xH 2 O, which led to 13 new metal–acetate polymeric complexes identified by single-crystal X-ray diffraction. We found that the diversity in coordination modes of the simple acetate ligand that interfere with substitution of the softer N donors led to several readily crystallizable complexes forming two distinct groups with respect to f-element interaction with the ionic liquid precursors. When the acidic/basic azole ratio was 1:3, acetate and a neutral basic azole were found to be coordinated to the metal centers but no water, although in one case (2) water was observed in the secondary coordination sphere: [Ce(μ 2 -OAc) 3 (C 1 im)] n (1, C 1 im = 1-methylimidazole), [Nd(μ 2 -(OAc) 3 (C 1 im)] n ·nH 2 O (2), [Ce(μ 2 -OAc) 3 (C 2 im)] n (3, C 2 im = 1-ethylimidazole), [Ln(μ 2 -OAc) 3 DMF] n (Ln = Nd (4), Ce (5); dimethylformamide (DMF) was substituted for the azole mixture), and [Nd(μ 2 -OAc) 3 (C 4 im)] n (6, C 4 im = 1-butylimidazole). However, when the stoichiometric ratio was 1:1, water was always observed coordinated to the metal ions with the acidic azole included in the structure as a solvate or cocrystal, despite a higher reaction temperature: [Nd(μ 2 -OAc) 3 (OH 2 )] n ·n(1,2,3-Taz) (7, 1,2,3-Taz = 1,2,3-triazole), [Ln(μ 2 -OAc) 3 (OH 2 )] n ·n(4,5-DCim) (Ln = Nd (8), Ce (9), 4,5-DCim = 4,5-dicyanoimidazole), [Ln(μ 2 -OAc) 3 (OH 2 )] n ·n(3,5-diNH 2 -1,2,4-Taz) (Ln = Nd (10), Ce (11), 3,5-diNH 2 -1,2,4-Taz = 3,5-diamino-1,2,4-triazole), [Ce(μ 2 -OAc) 3 (OH 2 )] n ·n(3-NH 2 -1,2,4-Taz) (12, 3-NH 2 -1,2,4-Taz = 3-amino-1,2,4-triazole), and [Nd(μ 2 -OAc) 3 (OH 2 )] n ·n(5-NH 2 -Tz) (13, 5-NH2-Tz = 5-aminotetrazole). All of the compounds retain the Ln:OAc– ratio of 1:3 and form 1D polymeric chains; however, they exhibit a variety of coordination modes affecting the degree of chain condensation. The isolation of both hydrated and anhydrous products revealed different abilities of the investigated soft N-donors to compete with O-donors finding their place in the coordination sphere of the lanthanide or in the crystal lattice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Determining the Oxygen Stoichiometry of Cobaltite Thin Films

Transition metal oxides (TMO) are promising materials to realize low-power neuromorphic devices. Their physical properties critically depend on their oxygen vacancy concentrations, whose experimental determination remains a challenging task. Here we focus on cobaltites, in particular La 1-x Sr x CoO 3-d (LSCO), and we present a strategy to identify fingerprints of oxygen vacancies in X-ray absorption (XA) spectra. Using a combination of experiment and theory, we show that the variation of the oxygen vacancy concentration in the perovskite phase of LSCO is correlated with the change of the relative peak positions of the O K-edge XA spectra. Furthermore, we also identify an additional geometrical fingerprint that captures both the changes of the Co-O bond length and Co-O-Co bond angle in the material due to the presence of oxygen vacancies. Finally, we predict the oxygen vacancy concentration of experimental samples and show how the resistivity of the oxide material may be tuned as a function of the defect concentration present in the system.

36 MATERIALS SCIENCE↗