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At least 145 records · Page 8

Thermally induced PtOx interfacial layer enhances stability of Pt/β-Ga2O3 vertical Schottky diodes

This study investigates the long-term stability of Pt/β-Ga2O3 field-plated Schottky barrier diodes at high temperatures, with extended thermal cycling and soaking stress. The device characteristics reveal a strong dependence on operating temperature, leading to an ON/OFF current ratio of ∼10× at ±3 V and 600 °C. Extensive thermal cycling (25 cycles over 100 h) between room temperature and 350 °C shows that leakage currents stabilize after the initial ten cycles. This stabilization is likely due to the formation of a thin PtOx layer at the Pt/β-Ga2O3 interface, as confirmed by high-resolution scanning transmission electron microscopy. Further exposure to a constant 350 °C environment for 10 h reveals a slight increase in the leakage current from 10−7 to 10−6 A at −5 V and degradation of the forward current, due to potential thermodynamic instability of the Ohmic contacts. This study provides insights into the changes in the Pt/β-Ga2O3 diode performance with thermal stress, offering a basis for predicting the device’s operational reliability at high temperatures for sensing and power applications.

08 HYDROGEN↗

High-resolution measurements of microphysics and entrainment in marine stratocumulus clouds

High-resolution measurements from the Airborne Cloud-Turbulence Observation System (ACTOS) during the Azores Stratocumulus Measurements of Radiation, Turbulence and Aerosols (ACORES) campaign are analysed for an investigation of the vertical profiles of microphysical properties and entrainment velocity ( W e ) in marine stratocumulus clouds. Here, the vertical profiles show the transition from the cloudy layer to free troposphere with nearly linear profiles of total water mixing ratio, liquid water potential temperature and virtual potential temperature, but the thickness of entrainment interfacial layer varies significantly. Sharp transitions of cloud microphysical and optical properties within a single horizontal flight leg are found in one stratocumulus cloud system. They seem to be related to the local environmental conditions, such as the wind shear and turbulent dissipation rate. W e values estimated by three methods show consistent tendencies in general and are clearly related to the local environmental conditions, such as vertical shear of the horizontal wind and turbulence intensity. However, the magnitudes of W e values differ by up to two orders of magnitude depending on the methods, which suggests that the estimation of W e from in situ measurements is still a challenge. Analysis of the microphysical response to entrainment suggests that inhomogeneous mixing occurs dominantly. On the other hand, the analysis results for the clouds under more humid conditions indicate a higher likelihood of homogeneous mixing.

54 ENVIRONMENTAL SCIENCES↗

Decoupling electrode kinetics to elucidate reaction mechanisms in alkaline water electrolysis

Alkaline water electrolysis (AWE) presents key advantages, including reduced material costs, enhanced operational stability, and compatibility with non-precious metal catalysts, positioning it as a scalable route for hydrogen production. In this study, we introduce a minimally invasive single-cell configuration incorporating a reference electrode via diaphragm extension to form an internal ion channel. This setup, combined with an interfaced potentiostat and auxiliary electrometer, enables real-time, independent monitoring of anode and cathode behavior, offering high-resolution electrochemical diagnostics. While it is well established that the hydrogen evolution reaction (HER) exhibits sluggish kinetics in alkaline media, our study reveals that this limitation persists even in practical AWE systems where nickel-based substrates are used as electrodes. This observation is supported by both experimental data and voltage breakdown modeling. Arrhenius-type analysis reveals that localized electric fields induced by catalysts shift the reaction kinetics from classical Butler–Volmer behavior toward a Marcus-like regime, where interfacial molecular dynamics and bimolecular charge transfer dominate. We propose a semi-empirical model and a surficial reaction mechanism to describe these dynamics. This work underscores the critical need for cathode innovation and provides a rational framework for designing advanced catalysts and electrode architectures to optimize AWE performance.

08 HYDROGEN↗

Correlative analysis of structure and chemistry of Li x FePO 4 platelets using 4D-STEM and X-ray ptychography

Lithium iron phosphate (Li x FePO 4 ), a cathode material used in rechargeable Li-ion batteries, phase separates upon de/lithiation under equilibrium. The interfacial structure and chemistry within these cathode materials affects Li-ion transport, and therefore battery performance. Here, correlative imaging of Li x FePO 4 was performed using four-dimensional scanning transmission electron microscopy (4D-STEM), scanning transmission X-ray microscopy (STXM), and X-ray ptychography in order to analyze the local structure and chemistry of the same particle set. Over 50,000 diffraction patterns from 10 particles provided measurements of both structure and chemistry at a nanoscale spatial resolution (16.6–49.5 nm) over wide (several micron) fields-of-view with statistical robustness. Li x FePO 4 particles at varying stages of delithiation were measured to examine the evolution of structure and chemistry as a function of delithiation. In lithiated and delithiated particles, local variations were observed in the degree of lithiation even while local lattice structures remained comparatively constant, and calculation of linear coefficients of chemical expansion suggest pinning of the lattice structures in these populations. Partially delithiated particles displayed broadly core–shell-like structures, however, with highly variable behavior both locally and per individual particle that exhibited distinctive intermediate regions at the interface between phases, and pockets within the lithiated core that correspond to FePO 4 in structure and chemistry. The results provide insight into the Li x FePO 4 system, subtleties in the scope and applicability of Vegard’s law (linear lattice parameter-composition behavior) under local versus global measurements, and demonstrate a powerful new combination of experimental and analytical modalities for bridging the crucial gap between local and statistical characterization.

25 ENERGY STORAGE↗

Electron ptychography reveals a ferroelectricity dominated by anion displacements

Sodium niobate, a lead-free ferroic material, hosts delicately balanced, competing order parameters, including ferroelectric states that can be stabilized by epitaxial strain. Here we show that the resulting macroscopic ferroelectricity exhibits an unconventional microscopic structure using multislice electron ptychography. This technique overcomes multiple scattering artefacts limiting conventional electron microscopy, enabling both lateral spatial resolution beyond the diffraction limit and recovery of three-dimensional structural information. These imaging capabilities allow us to separate the ferroelectric interior of the sample from the relaxed surface structure and identify the soft phonon mode and related structural distortions with picometre precision. Unlike conventional ferroelectric perovskites, we find that the polar distortion in this material involves minimal distortions of the cation sublattices and is instead dominated by anion displacements relative to the niobium sublattice. We establish limits on film thickness for interfacial octahedral rotation engineering and directly visualize a random octahedral rotation pattern, arising from the flat dispersion of the associated phonon mode.

ferroelectrics and multiferroics↗

In Situ Cyclized Polyacrylonitrile Coating: Key to Stabilizing Porous High-Entropy Oxide Anodes for High-Performance Lithium-Ion Batteries

High-entropy oxides (HEOs) composed of multiple metal elements have attracted great attention as anode materials for lithium-ion batteries (LIBs) due to the synergistic effects of various metal species. However, the practical applications of HEOs are still plagued by poor conductivity, unstable solid electrolyte interphase (SEI) and poor cycling stability. In this work, nanosized (FeCoNiCrMn) 3 O 4 HEO (NHEO) is prepared successfully by the NaCl-assisted mechanical ball-milling strategy. Novelly, polyacrylonitrile (PAN) is used as the binder and then in situ thermochemically cyclized to construct a cyclized PAN (cPAN) outer layer onto NHEO (NHEO-cPAN). The in situ formed cPAN coating not only improves the electrical conductivity, but also reinforces the structural and interfacial stability, and thereby, the resulted NHEO-cPAN electrode exhibits significantly enhanced rate and cyclic performance. Specifically, NHEO-PAN500 electrode delivers a high reversible capacity of 560 mAh g –1 at 5 A g –1 and a high-capacity retention of 83% over 800 cycles at 3 A g –1 . Furthermore, the structural evolution and electrochemical behavior of NHEO-PAN electrode during discharge/charge is systematically investigated by operando X-ray diffraction, in situ impedance spectroscopy and ex situ high-resolution transmission electron microscopy. Therefore, this work provides new insights into the engineering of electrode and interphase for high-performance HEO electrode materials, potentially enlightening the practical applications of HEO-based LIBs.

25 ENERGY STORAGE↗

A Multiscale Simulation Study of Influence of Morphology on Ion Transport in Block Copolymeric Ionic Liquids

In this work, we present results of a multiscale simulation study involving coarse-graining and reverse-mapping steps probing at an atomistic resolution the influence of morphology on ion transport in block copolymer polymeric ionic liquids. We provide a detailed description of the multiscale simulation methodology and then describe the results in the context of four microphase-separated morphologies: two lamella systems, a cylinder, and a gyroid morphology. For the framework adopted in this study (in which the total number of ions was maintained fixed), morphology had little influence on the fraction of ions segregating to the interface and the coordination and hopping characteristics of such interfacially present ions. Such results manifested in anion mobilities being insensitive to the morphology once the dimensionality of the morphology was accounted for. Overall, our results are consistent with the hypothesis that the mobility of ions in such microphase-separated morphologies, after accounting for the dimensionality effects, can be roughly correlated to a linear superposition based on the fraction of bulk anions, which possess mobilities unperturbed from their values in the conducting homopolymers, and the interfacial anions, which exhibit much lower mobilities.

36 MATERIALS SCIENCE↗

Emergence of complex-regular eutectic patterns in Al–Ge: Observations from correlative nano-imaging

Eutectic solidification exemplifies nonequilibrium pattern formation, making it a well-studied moving boundary problem. Yet the mechanisms behind the formation of complex-regular microstructures – particularly in highly anisotropic systems with a significant volume fraction of a faceted phase – remain poorly understood. Our understanding of such systems is made complicated by the nonlinear interface kinetics and unique growth dynamics characteristic of faceted phases. To address these challenges, we investigate a model Al–Ge eutectic system, where the faceted Ge phase constitutes a substantial volume fraction (~0.35) and where the two solid phases arrange into so-called “fishbone” or “feather” complex-regular patterns. Using synchrotron-based x-ray nano-imaging and nanotomography with high spatial resolution (22 nm per pixel), we capture in real-time the evolution of the solid–liquid interfaces and the resulting three-dimensional microstructures in this faceted/non-faceted eutectic system. By integrating these observations with electron backscattered diffraction, we elucidate the crystallographic biases on the solidification process and the mechanisms driving the formation of such complex-regular microstructures. These findings inform a new growth model for irregular eutectics in (near-)symmetrical phase diagrams, offering insight on advanced microstructural design and processing strategies. More broadly, we demonstrate how interfacial curvature is generated in irregular eutectic alloys and how it depends on the volume fraction of the faceted phase.

36 MATERIALS SCIENCE↗

Polyolefin blends with co-continuous architectures enabled by dynamic covalent crosslinking

Blending polymers produces brittle materials due to macrophase separation and poor interfacial adhesion, which is exemplified by mixtures of polyolefins. This presents a formidable challenge for the mechanical recycling of mixed plastic waste. Here, we demonstrate that dynamic covalent crosslinking of immiscible polyolefin blends creates macrophase separated co-continuous architectures, yet they display excellent mechanical properties, which challenges the conventional wisdom regarding morphology-property relationships in polymer blend compatibilization. We find that the position and orientation of dynamic crosslinks and their influence on crystallinity are key to understanding the structure-morphology-property relationships. In particular, high-resolution microscopy imaging reveals alignment of crystallite planes with strong orientational preference, particularly at polymer-polymer interfaces, which contribute to material performance. We further demonstrate that changes in crosslinker density and valency allow the properties of binary and ternary polyolefin blends to be tuned in a modular fashion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Natural organic matter composition and nanomaterial surface coating determine the nature of platinum nanomaterial-natural organic matter corona

Natural organic matter corona (NOM corona) is an interfacial area between nanomaterials (NMs) and the sur- rounding environment, which gives rise to NMs' unique surface identity. While the importance of the formation of natural organic matter (NOM) corona on engineered nanomaterials (NMs) to NM behavior, fate, and toxicity has been well-established, the understanding of how NOM molecular properties affect NOM corona composition remains elusive due to the complexity and heterogeneity of NOM. This is further complicated by the variation of NOMs from different origins. Here we use eight NOM isolates of different molecular composition and ultrahigh resolution Fourier-transform ion cyclotron resonance-mass spectrometry (ESI-FT-ICR-MS) to determine the mol- ecular composition of platinum NM-NOM corona as a function of NOM composition and NM surface coating. We observed that the composition of PtNM-NOM corona varied with the composition of the original NOM. The per- centage of NOM formulas that formed PVP-PtNM-NOM corona was higher than those formed citrate-PtNM-NOM corona, due to increased sorption of NOM formulas, in particular condensed hydrocarbons, to the PVP coating. The relative abundance of heteroatom formulas (CHON, CHOS, and CHOP) was higher in the PVP-PtNM-NOM corona than in citrate-PtNM-corona which was in turn higher than those in the original NOM isolate, indicating preferential partitioning of heteroatom-rich molecules to NM surfaces. The relative abundance of CHO, CHON, CHOS, CHOP and condensed hydrocarbons in PtNM-NOM corona increased with their increase in NOM isolates. Furthermore, PtNM-NOM corona is rich with compounds with high molecular weight. This study demonstrates that the composition and properties of PtNM-NOM corona depend on NOM molecular properties and PtNM sur- face coating. The results here provide evidence of molecular interactions between NOM and NMs, which are crit- ical to understanding NM colloidal properties (e.g., surface charge and stability), interaction forces (e.g., van der Waals and hydrphobic), environmental behaviors (e.g., aggregation, disso.

Baalousha, Mohammed↗

Direct Optical Lithography of Colloidal Metal Oxide Nanomaterials for Diffractive Optical Elements with 2π Phase Control

Spatially patterned dielectric materials are ubiquitous in electronic, photonic, and optoelectronic devices. These patterns are typically made by subtractive or additive approaches utilizing vapor-phase reagents. On the other hand, recent advances in solution-phase synthesis of oxide nanomaterials have unlocked a materials library with greater compositional, microstructural, and interfacial tunability. However, methods to pattern and integrate these nanomaterials in real-world devices are less established. In this work, we directly optically pattern oxide nanoparticles (NPs) by mixing them with photosensitive diazo-2-naphthol-4-sulfonic acid and irradiating with widely available 405 nm light. We demonstrate the direct optical lithography of ZrO 2 , TiO 2 , HfO 2 , and ITO NPs and investigate the chemical and physical changes responsible for this photoinduced decrease in solubility. Micron-thick layers of amorphous ZrO 2 NPs were patterned with micron resolution and shown to allow 2 pi phase control of visible light. We also show multilayer patterning and use it to fabricate features with different thicknesses and distinct structural colors. Upon annealing at 400 degrees C, the deposited ZrO 2 structures have excellent optical transparency across a wide wavelength range (0.3-10 mu m), a high refractive index (n = 1.84 at 633 nm), and are optically smooth. We then fabricate diffractive optical elements, such as binary phase diffraction gratings, that show efficient diffractive behavior and good thermal stability. Different oxide NPs can also be mixed prior to patterning, providing a high level of material tunability. This work demonstrates a general patterning approach that harnesses the processability and diversity of colloidal oxide nanomaterials for use in photonic applications.

2𝜋 phase shift↗

Irradiation-induced amorphization of UO 2 films prepared by spraying-assisted combustion synthesis

Spraying-assisted combustion synthesis with uranyl nitrate – acetylacetone – 2-methoxyethanol solutions was used to prepare UO 2 films on an aluminum alloy substrate. The tuning of the spraying parameters and annealing temperatures allowed the preparation of UO 2 films with thicknesses varying from 10–300 nm and 5–10 nm UO 2 grain size. High-resolution electron microscopy and X-ray photoelectron spectroscopy showed that increasing the annealing temperature promotes Mg diffusion from the substrate into the films. The incorporation of Mg reduced the overall crystallinity of the films. The irradiation with Ar 2+ ions (1.7 MeV energy and a fluence of 2 × 10 16 ions/cm 2 ) did not degrade the quality of the films. However, the Mg content significantly influenced the irradiation-induced restructuring of the UO 2 films. Irradiated films with low or no Mg content exhibit high crystallinity, and the UO 2 /Al interfacial layer becomes highly porous. Films with higher Mg content are mostly amorphized after irradiation. The origin of irradiation-induced amorphization was related to the formation of Mg y U 1-y O 2±x solid solutions. Chemically complex, pore-free, and amorphous Mg-Al-O film/substrate interfacial layers enable continuous Mg diffusion during irradiation. As a result, the gradual increase in Mg amounts triggers irradiation-induced precipitation of a crystalline MgO-rich phase within the amorphous films.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Carbide-Modified Pd on ZrO2 as Active Phase for CO2-Reforming of Methane—A Model Phase Boundary Approach

Starting from subsurface Zr0-doped “inverse” Pd and bulk-intermetallic Pd0Zr0 model catalyst precursors, we investigated the dry reforming reaction of methane (DRM) using synchrotron-based near ambient pressure in-situ X-ray photoelectron spectroscopy (NAP-XPS), in-situ X-ray diffraction and catalytic testing in an ultrahigh-vacuum-compatible recirculating batch reactor cell. Both intermetallic precursors develop a Pd0–ZrO2 phase boundary under realistic DRM conditions, whereby the oxidative segregation of ZrO2 from bulk intermetallic PdxZry leads to a highly active composite layer of carbide-modified Pd0 metal nanoparticles in contact with tetragonal ZrO2. This active state exhibits reaction rates exceeding those of a conventional supported Pd–ZrO2 reference catalyst and its high activity is unambiguously linked to the fast conversion of the highly reactive carbidic/dissolved C-species inside Pd0 toward CO at the Pd/ZrO2 phase boundary, which serves the role of providing efficient CO2 activation sites. In contrast, the near-surface intermetallic precursor decomposes toward ZrO2 islands at the surface of a quasi-infinite Pd0 metal bulk. Strongly delayed Pd carbide accumulation and thus carbon resegregation under reaction conditions leads to a much less active interfacial ZrO2–Pd0 state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantification of morphological change in materials based on image data utilizing machine learning techniques

Computed tomography (CT) resolution has become high enough to monitor morphological changes due to aging in materials in long-term applications. We explored the utility of the critic of a generative adversarial network (GAN) to automatically detect such changes. The GAN was trained with images of pristine Pharmatose, which is used as a surrogate energetic material. It is important to note that images of the material with altered morphology were only used during the test phase. The GAN-generated images visually reproduced the microstructure of Pharmatose well, although some unrealistic particle fusion was seen. Calculated morphological metrics (volume fraction, interfacial line length, and local thickness) for the synthetic images also showed good agreement with the training data, albeit with signs of mode collapse in the interfacial line length. While the critic exposed changes in particle size, it showed limited ability to distinguish images by particle shape. The detection of shape differences was also a more challenging task for the selected morphological metrics that related to energetic material performance. We further tested the critic with images of aged Pharmatose. Subtle changes due to aging are difficult for the human analyst to detect. Both critic and morphological metrics analysis showed image differentiation.

36 MATERIALS SCIENCE↗

Utilization of the Critic Subnetwork of a Generative Adversarial Network as Detector of Morphological Material Change in Image Data

The resolution of computed tomography (CT) has become high enough to monitor morphological changes due to aging in materials in long-term applications. For this work, we explored the utility of the critic of a generative adversarial network (GAN) to automatically detect such changes. The GAN was trained with images of pristine Pharmatose, which is used as a surrogate energetic material. It is important to note that images of the material with altered morphology were only used during the test phase. The GAN-generated images reproduced the microstructure of Pharmatose well, although some unrealistic particle fusion was seen. Calculated morphological metrics (volume fraction, interfacial line length, and local thickness) for the synthetic images also showed good agreement with the training data, albeit with signs of mode collapse in the interfacial line length. While the critic exposed changes in particle size, it showed limited ability to distinguish images by particle shape. The detection of shape differences was also a more challenging task for the selected morphological metrics that related to energetic material performance. We further tested the critic with images of aged Pharmatose. Subtle changes due to aging are difficult for the human analyst to detect; but both critic and morphological metrics analysis showed image differentiation.

36 MATERIALS SCIENCE↗

Additive Manufacturing of Thermal Energy Storage Composites with Microencapsulated Phase Change Materials Supported in a Multipolymer Matrix

Additive manufacturing (AM) techniques to directly integrate phase change materials (PCMs) are of interest for efficient thermal energy storage (TES) architectures. Complex, high surface-to-volume ratio composites embedded with PCM can improve thermal management with reduced material waste for customizable device fabrication. Reducing feature sizes of TES-integrated heat exchangers using AM can increase heat transfer without thermal conductivity enhancement. Here, composite AM materials containing 60 wt% microencapsulated phase change materials (MEPCM) are fabricated using off-the-shelf printers at common speeds and resolutions. High MEPCM loading in filaments is achieved with powder extrusion using two polymers, thermoplastic-polyurethane (TPU) and polycaprolactone (PCL), that mediate flexibility and rigidity for effective extrusion and printing without filament fracture or buckling. Furthermore, with PCL and TPU at 20 wt% each and 60 wt% MEPCM (P 20 T 20 M 60 ), smooth, form-stable filaments are consistently printed. Powder-based extrusion displays negligible damaging effects on the MEPCM. Printed P 20 T 20 M 60 demonstrates 105 J/g of energy storage with no degradation through 250 thermal cycles, within 5% of the theoretical storage enthalpy. Combining PCL/TPU shows good interfacial adhesion between print layers and produces high surface area objects, like 15% gyroids, and dense, 100% infilled pucks. Prints are also scalable to a 900 cm 3 honeycomb heat exchanger with an estimated 9 Wh energy storage.

25 ENERGY STORAGE↗

Impact of Dilute DIO Additive on Local Microstructure of Fluorinated, pNDI‐Based Polymer Solar Cells

The performance of all‐polymer solar cells is often enhanced by incorporating solvent additives during solution processing. Here, in particular, blends based on the model all‐polymer system PBDBT:N2200 have been shown to have increased short‐circuit current and fill factor when processed with dilute diiodooctane (DIO). However, the morphological mechanism that drives the increase in performance is often not well understood due to limitations in common characterization techniques. In this study, it is shown that a combination of X‐ray techniques with cryogenic high‐resolution transmission electron microscopy (HRTEM) analysis can provide a quantitative and spatially resolved picture of polymer chain orientation and alignment in all‐polymer blends. It is found that DIO induces vertical phase separation in PBDBT‐2F:F‐N2200 and increases donor crystallite thickness in the pi‐stacking direction leading to an acceptor‐rich film surface. However, it is also shown that DIO does not disrupt the formation of face‐on donor–acceptor interfaces. These findings suggest that dilute DIO primarily affects crystalline domain formation in single component regions as opposed to mixed regions; thus, dilute DIO can impact vertical charge transport pathways without sacrificing donor–acceptor interfacial connectivity.

Cheng, Christina↗

Observations of grain-boundary phase transformations in an elemental metal

The theory of grain boundary (the interface between crystallites, GB) structure has a long history 1 and the concept of GBs undergoing phase transformations was proposed 50 years ago 2,3 . The underlying assumption was that multiple stable and metastable states exist for different GB orientations 4,5,6 . The terminology ‘complexion’ was recently proposed to distinguish between interfacial states that differ in any equilibrium thermodynamic property 7 . Different types of complexion and transitions between complexions have been characterized, mostly in binary or multicomponent systems 8,9,10,11,12,13,14,15,16,17,18,19 . Simulations have provided insight into the phase behaviour of interfaces and shown that GB transitions can occur in many material systems 20,21,22,23,24 . However, the direct experimental observation and transformation kinetics of GBs in an elemental metal have remained elusive. In this work we demonstrate atomic-scale GB phase coexistence and transformations at symmetric and asymmetric $[11\bar{1}]$ tilt GBs in elemental copper. Atomic-resolution imaging reveals the coexistence of two different structures at Σ19b GBs (where Σ19 is the density of coincident sites and b is a GB variant), in agreement with evolutionary GB structure search and clustering analysis 21,25,26 . We also use finite-temperature molecular dynamics simulations to explore the coexistence and transformation kinetics of these GB phases. Our results demonstrate how GB phases can be kinetically trapped, enabling atomic-scale room-temperature observations. Our work paves the way for atomic-scale in situ studies of metallic GB phase transformations, which were previously detected only indirectly 9,15,27,28,29 , through their influence on abnormal grain growth, non-Arrhenius-type diffusion or liquid metal embrittlement.

36 MATERIALS SCIENCE↗