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At least 343 records · Page 19

Making Plasticized Polymer Electrolytes Stable Against Sodium Metal for High‐Energy Solid‐State Sodium Batteries

Abstract Solid polymer electrolytes based on plastic crystals are promising for solid‐state sodium metal (Na 0 ) batteries, yet their practicality has been hindered by the notorious Na 0 ‐electrolyte interface instability issue, the underlying cause of which remains poorly understood. Here, by leveraging a model plasticized polymer electrolyte based on conventional succinonitrile plastic crystals, we uncover its failure origin in Na 0 batteries is associated with the formation of a thick and non‐uniform solid electrolyte interphase (SEI) and whiskery Na 0 nucleation/growth. Furthermore, we design a new additive‐embedded plasticized polymer electrolyte to manipulate the Na 0 deposition and SEI formulation. For the first time, we demonstrate that introducing fluoroethylene carbonate (FEC) additive into the succinonitrile‐plasticized polymer electrolyte can effectively protect Na 0 against interfacial corrosion by facilitating the growth of dome‐like Na 0 with thin, amorphous, and fluorine‐rich SEIs, thus enabling significantly improved performances of Na//Na symmetric cells (1,800 h at 0.5 mA cm −2 ) and Na//Na 3 V 2 (PO 4 ) 3 full cells (93.0 % capacity retention after 1,200 cycles at 1 C rate in coin cells and 93.1 % capacity retention after 250 cycles at C/3 in pouch cells at room temperature). Our work provides valuable insights into the interfacial failure of plasticized polymer electrolytes and offers a promising solution to resolving the interfacial instability issue.

Zou, Peichao↗

Ice Recrystallization Inhibition Activity of Soy Protein Hydrolysates

Identifying and developing ice recrystallization inhibitors from sustainable food proteins such as soy protein isolate (SPI) can lead to practical applications in both pharmaceutical and food industries. Here, the objective of this study was to investigate the ice recrystallization inhibition (IRI) activity of SPI hydrolysates, and this was achieved by using an IRI activity-guided fractionation approach and relating IRI activity to interfacial molecular activity measured by vibrational sum frequency generation (VSFG). In addition, the impact of molecular weight (MW) and enzyme specificity was analyzed using three different proteases (Alcalase, trypsin, and pancreatin) and varying hydrolysis times. Using preparative chromatography, hydrolysates from each enzyme treatment were fractionated into five different MW fractions (F1–F5), which were then characterized by high-performance liquid chromatography (HPLC). All SPI hydrolysates had IRI activity, resulting in a 57–29% ice crystal diameter reduction when compared to native SPI. The F1 fraction (of 4–14 kDa) was most effective among all tested hydrolysates, while the lower MW peptide fractions lacked activity. One sample (SPI-ALC 20-F1) had a 52% reduction of ice crystal size at a lower concentration of 2% compared to the typical 4% used. SFG showed a difference in H-bonding and hydrophobic interactions of the molecules on the water/air interface, which may be linked to IRI activity. This study demonstrates for the first time the ability of SPI hydrolysates to inhibit ice crystal growth and the potential application of SFG to study molecular interaction at the interface that may help illustrate the mechanism of action.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Making Plasticized Polymer Electrolytes Stable Against Sodium Metal for High‐Energy Solid‐State Sodium Batteries

Solid polymer electrolytes based on plastic crystals are promising for solid-state sodium metal (Na 0 ) batteries, yet their practicality has been hindered by the notorious Na 0 -electrolyte interface instability issue, the underlying cause of which remains poorly understood. Here, in this study, by leveraging a model plasticized polymer electrolyte based on conventional succinonitrile plastic crystals, we uncover its failure origin in Na 0 batteries is associated with the formation of a thick and non-uniform solid electrolyte interphase (SEI) and whiskery Na 0 nucleation/growth. Furthermore, we design a new additive-embedded plasticized polymer electrolyte to manipulate the Na 0 deposition and SEI formulation. For the first time, we demonstrate that introducing fluoroethylene carbonate (FEC) additive into the succinonitrile-plasticized polymer electrolyte can effectively protect Na 0 against interfacial corrosion by facilitating the growth of dome-like Na 0 with thin, amorphous, and fluorine-rich SEIs, thus enabling significantly improved performances of Na//Na symmetric cells (1,800 h at 0.5 mA cm −2 ) and Na//Na 3 V 2 (PO 4 ) 3 full cells (93.0 % capacity retention after 1,200 cycles at 1 C rate in coin cells and 93.1 % capacity retention after 250 cycles at C/3 in pouch cells at room temperature). Our work provides valuable insights into the interfacial failure of plasticized polymer electrolytes and offers a promising solution to resolving the interfacial instability issue.

25 ENERGY STORAGE↗

Understanding the effect of crystal anisotropy on grain growth, texturing and transport via the orthorhombic ?-U system [Slides]

The alpha phase of uranium exhibits the orthorhombic crystal structure, resulting in significant physical property anisotropy. These complex properties make the material challenging to work with in engineering settings but provide a rich arena to investigate the fundamental, multi-scale effects of anisotropy on physical behaviors such as grain growth and microstructure evolution under irradiation. We apply molecular dynamics and phase field modeling to study mass transport and grain growth in alpha-uranium. We characterize the mobilities of crystalline defects and the interfacial energy, and We find that the grain boundary energy is highly variable depending on the interface structure and that the relative rates of defect transport change with temperature. We also find that anisotropic thermal expansion has a significant impact on grain growth kinetics and texture development. Our results are used to explain experimental observations and to provide a basis for further hypotheses into the complex physical behavior of alpha-uranium.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The dependence of aluminum lattice orientation on semiconductor lattice parameter in planar InAs/Al hybrid heterostructures

We present a detailed study of 7-nm thick Al layers epitaxially grown on In x Al 1-x As or Al 1-x Ga x Sb y As 1-y (0 0 1) semiconductors using high-resolution transmission electron microscopy (HRTEM) and synchrotron X-ray diffraction (XRD). These techniques provide high spatial and high reciprocal space resolution information about Al lattice orientations and interfacial structure, highlighting the existence of a strong correlation between the surface lattice parameter of the semiconductor and the normal orientation of the aluminum film. The normal orientation of Al layers is found to be [1 1 1] when the in-plane semiconductor surface lattice parameter, a S , is smaller than 5.98 Å, and is [1 1 0] when aS is larger than this value. In the transition between these lattice parameters where one orientation is preferred, both orientations may be observed. Concomitant with the change in normal orientation is an inversion in the strain state of the aluminum film. When the normal orientation is [1 1 1], the Al film is compressively strained; while for [1 1 0] normal orientations, the Al in-plane strain is tensile. An energy balance model, accounting for surface, interfacial, side-face, and strain energy, and the registry of lattice planes across the semiconductor/aluminum interface provide explanations for the observed normal orientation and strain inversion.

36 MATERIALS SCIENCE↗

Thickness and temperature dependence of the atomic-scale structure of SrRuO 3 thin films

The temperature-dependent layer-resolved structure of 3 to 44 unit cell thick SrRuO 3 (SRO) films grown on Nb-doped SrTiO 3 substrates is investigated using a combination of high-resolution synchrotron x-ray diffraction and high-resolution electron microscopy to understand the role that structural distortions play in suppressing ferromagnetism in ultra-thin SRO films. The oxygen octahedral tilts and rotations and Sr displacements characteristic of the bulk orthorhombic phase are found to be strongly dependent on temperature, the film thickness, and the distance away from the film–substrate interface. For thicknesses, t, above the critical thickness for ferromagnetism (t > 3 uc), the orthorhombic distortions decrease with increasing temperature above T C . Below T C , the structure of the films remains constant due to the magneto-structural coupling observed in bulk SRO. The orthorhombic distortions are found to be suppressed in the 2–3 interfacial layers due to structural coupling with the SrTiO 3 substrate and correlate with the critical thickness for ferromagnetism in uncapped SRO films.

36 MATERIALS SCIENCE↗

Structural Implications of Interfacial Hydrogen Bonding in Hydrated Wyoming-Montmorillonite Clay

Montmorillonite (MMT) clay - a layered porous nanomaterial used as seals in engineered waste containment barriers for spent nuclear fuel - adopts discrete hydration/swelling states depending upon surrounding water and ion activities and confining pressure. The structure of nanoconfined water and charge-balancing counterions in the clay mineral interlayers dictate the swelling and mechanical behavior of MMT, so a molecular model for this clay with high structural fidelity is required to accurately predict the reliability of long-term nuclear waste storage. Here, we present a molecular model for MMT that is based on high resolution transmission electron microscopy of Wyoming-MMT single crystals. Imaging data unambiguously show a cis-vacant arrangement of structural hydroxyl groups in the octahedral sheet, whereas existing molecular models assume a centrosymmetric trans-vacant configuration for MMT. Furthermore, using atomistic simulations, we find that the cis-vacant arrangement of structural hydroxyl groups significantly affects the structure of adsorbed water yielding a larger population of hydrogen bonds with bridging oxygens on the tetrahedral sheet and weak hydrogen bonding between the hydroxyl groups in the octahedral sheet and water in the clay mineral interlayers. As a result, water adsorbed in the interlayer is more "ice-like", with stronger ordering and lower density, although the diffusivity of the interlayer species is not significantly diminished. Our improved structural model for MMT provides insight into the energetics of water adsorption, which ultimately dictates its pore- to macro-scale swelling, transport, and fracture properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The mechanism of hydroxyapatite coatings degradation at high substrate temperatures

Physical vapor deposition methods used for hydroxyapatite (HA) coatings typically require elevated substrate temperatures and post-deposition annealing to induce crystallization. However, such thermal treatments can degrade both the mechanical integrity and bioactivity of the coating, particularly when substrate temperatures exceed 500 °C. The mechanisms underlying these phenomena remain insufficiently understood. In this study, HA thin films were deposited on silicon and Ti6Al4V substrates using pulsed laser deposition and were systematically characterized to elucidate these mechanisms. XPS and SIMS analyses revealed a temperature-dependent loss of OH − and PO 4 3− groups, an increased Ca/P ratio, and the formation of interfacial oxides, all of which contribute to weakened adhesion. To clarify the temperature-dependent decline in bioactivity, protein adsorption behavior was analyzed using a Kramers-type kinetic framework; the fitted desorption kinetics indicate that coatings deposited near ∼500 °C provide the most stable protein attachment, whereas higher temperatures accelerate desorption due to dehydroxylation and carbonate substitution. Together, these findings provide mechanistic insight into the thermal degradation of HA coatings and offer a framework for optimizing deposition parameters to preserve stoichiometry, adhesion, and bioactivity for long-term biomedical applications.

Kylychbekov, Salizhan [Univ. of Oxford (United Kin↗

Uptake of Pb and the Formation of Mixed (Ba,Pb)SO 4 Monolayers on Barite During Cyclic Exposure to Lead-Containing Sulfuric Acid

Barite (BaSO 4 ) is a common additive in lead-acid batteries, where it acts as a nucleating agent to promote the reversible formation and dissolution of PbSO 4 during battery cycling. However, little is known about the molecular-scale mechanisms the nucleation and cyclic evolution of PbSO 4 over a battery’s lifetime. In this study, we explore the responses of a barite (001) surface to cycles of high and low lead concentrations in the presence of 100 mM sulfuric acid using in-situ atomic force microscopy and high-resolution X-ray reflectivity. Here we find that PbSO 4 epitaxial films readily nucleate on the barite surface, even from solutions that are undersaturated relative to bulk PbSO 4 . Despite this, barite (001) proves to be an ineffective nucleator of bulk PbSO 4 , as multilayer growth is suppressed even in highly supersaturated solutions. Instead, we find evidence that Pb 2+ ions can directly exchange with Ba 2+ to create mixed (Ba,Pb)SO 4 surfaces. These chemically mixed surfaces do not host PbSO4 monolayers as readily as pristine barite, and the original reactivity is not regained until a fresh surface is reestablished by aggressive etching. Our results can be partly explained by traditional models of Stranski-Krastanov (S-K) growth, in which monolayer films are stabilized by a reduction in surface energy, but multilayer growth is inhibited by epitaxial strain. Complementary density functional theory calculations confirmed the basic energetic-terms of traditional S-K models, but also showed evidence form more complex, thickness-dependent, energetics than would be predicted from the S-K models. The experimental results can be better understood by extending the S-K model to consider the formation of mixed surfaces and films, which can have reduced strain and interfacial energies relative to pure films, while also being stabilized by entropy of mixing. These insights into non-stoichiometric heteroepitaxy will enable better predictions of how barite affects PbSO 4 nucleation in battery environments.

25 ENERGY STORAGE↗

In Situ Observation of Growth Dynamics in DECLIC Directional Solidification Insert Onboard ISS: DSI-R Flight Campaign

The study of solidification microstructure formation is of utmost importance for materials design and processing, as solid-liquid interface patterns largely govern mechanical and physical properties. Pattern selection occurs under dynamic conditions of growth in which the initial morphological instability evolves nonlinearly and undergoes a reorganization process. The dynamic and nonlinear nature of this instability renders in situ observation of the interface an invaluable tool to gain knowledge on the time-evolution of the interface pattern. Transparent organic analogs, which solidify like metallic alloys, allow direct visualization of interface dynamics. Extensive ground-based studies of both metallic and organic bulk samples have established the presence of significant convection during solidification processes that alters the formation of interfacial microstructures. A reduced-gravity environment is therefore mandatory for fluid flow elimination in bulk samples. In the framework of the CNES project MISOL3D (MIcrostrutures de SOLidification 3D) and the NASA projects DSIP (Dynamical Selection of 3D Interface Patterns), SPADES (SPAtiotemporal Evolution of three-dimensional DEndritic array Structures) and CAMUS (ComputAtional Studies of MicrostrUcture Formation During Alloy Solidification in Microgravity), we participated in the development of the Directional Solidification Insert (DSI) of the DEvice for the study of Critical Liquids and Crystallization (DECLIC). The DECLIC-DSI is dedicated to in situ and real-time characterization of solid-liquid interface patterns during directional solidification of transparent alloys in diffusive transport regime. Between April 2010 and March 2011, the first ISS campaign (DSI) explored the entire range of microstructures resulting in unprecedented observations. A second campaign (DSI-R), performed between October 2017 and December 2018, in which the insert contained an alloy of higher solute concentration, allowed to complete the benchmark database. The increase of solute concentration resulted in well-developed dendritic patterns at lower velocities (lower interface curvature and larger tip radius). The microstructure resulting from dendritic growth is dominant in metallurgy so that it is fundamental to understand the mechanisms of its formation. The main aims of this experimental campaign are to understand: the mechanisms of the cell to dendrite transition, the fundamental mechanisms of sidebranching formation, the dependence of dendrite tip shapes on growth conditions, the interaction of primary array and secondary sidebranches, and the influence of subgrain boundaries on the spatiotemporal organization of the array structure. Preparation, analysis and interpretation of the experiments performed onboard ISS are considerably enhanced by experiments performed on ground using thin-samples (Pr. Trivedi’s group) and phase-field simulations of microstructure formation in a diffuse growth regime (Pr. Karma’s group). In this summary, we will present an initial assessment of the results obtained during the DSI-R campaign. Nomenclature Vp: pulling velocity G: thermal gradient L: solidified length rtip: tip curvature radius Acronyms/Abbreviations CADMOS: Centre d'Aide au Développement des activités en Micro-pesanteur et des Opérations Spatiales CNES: Centre National d’Études Spatiales DECLIC: Device for the study of Critical LIquids and Crystallization DSI: Directional Solidification Insert DSI-R: Directional Solidification Insert - Refurbish ISS: International Space Station NASA: National Aeronautics and Space Administration PF: phase-field SCN: Succinonitrile 3D: three-dimensional

Mota, F.L.↗

Mesoscale Frank–Kasper Crystal Structures from Dendron Assembly by Controlling Core Apex Interactions

Single-component polymeric materials open up a great potential for self-assembly into mesoscale complex crystal structures that are known as Frank-Kasper (FK) phases. Predicting the packing structures of the soft-matter spheres, however, remains a challenge even when the molecular design is precisely known. Here, we investigate the role of the molecules' enthalpic interaction in determining the low-symmetry crystal structures. To this end, we synthesize architecturally asymmetric dendrons by varying their apex functionalities and examine the packing structures of the second-generation (G2) dendritic wedges. Our work shows that weakening the hydrogen bonding of the dendron apex makes the particles softer and smaller, and leads to the formation of various FK structures at lower temperatures, including the new observation of a FK C14 phase in the cone-shaped dendron systems. As a consequence of the free energy balance between the particle's interfacial tension and the chain's stretching, various packing structures are mainly tuned by designing the hydrogen bonding interaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ginzburg-Landau theory for the solid-liquid interface of bcc elements

Consideration is given to a simple order-parameter theory for the interfacial tension of body-centered-cubic solids in which the principal order parameter is the amplitude of the density wave at the smallest nonzero reciprocal-lattice vector of the solid. The parameters included in the theory are fitted to the measured heat of fusion, melting temperature, and solid-liquid density difference, and to the liquid structure factor and its temperature derivative at freezing. Good agreement is found with experiment for Na and Fe and the calculated anisotropy of the surface tension among different crystal faces is of the order of 2 percent. On the basis of various assumptions about the universal behavior of bcc crystals at melting, the formalism predicts that the surface tension is proportional to the heat of fusion per surface atom.

Shih, W. H.↗

Effect of Composite Fabrication on the Strength of Single Crystal Al2O3 Fibers in Two Fe-Base Alloy Composites

Continuous single-crystal Al2O3 fibers have been incorporated into a variety of metal and intermetallic matrices and the results have consistently indicated that the fiber strength had been reduced by 32 to 50% during processing. Two iron-based alloys, FeNiCoCrAl and FeAlVCMn, were chosen as matrices for Al2O3 fiber reinforced metal matrix composites (MMC) with the goal of maintaining Al2O3 fiber strength after composite processing. The feasibility of Al2O3/FeNiCoCrAl and Al2O3/FeAlVCMn composite systems for high temperature applications were assessed in terms of fiber-matrix chemical compatibility, interfacial bond strength, and composite tensile properties. The strength of etched-out fibers was significantly improved by choosing matrices containing less reactive elements. The ultimate tensile strength (UTS) values of the composites could generally be predicted with existing models using the strength of etched-out fibers. However, the UTS of the composites were less than desired due to a low fiber Weibull modulus. Acoustic emission analysis during tensile testing was a useful tool for determining the efficiency of the fibers in the composite and for determining the failure mechanism of the composites.

Draper, Susan L.↗

Effect of grain size on iron-boride nanoglasses

Metallic nanoglasses are made of amorphous grains that are separated by lower-density amorphous boundaries, which have been proposed to enhance plasticity through the deflection of cracks and shear bands at interfaces. It has been difficult to experimentally control grain size and interfacial structure to understand their roles in plastic deformation. Here, we fabricate bulk nanoglasses via compaction and sintering of colloidally synthesized amorphous iron-boride nanoparticles. These nanoglasses have amorphous grains with diameters from 116nm to 576nm and were tested using nanoindentation and micropillar compressions. The nanoglass with a grain size of 576 nm shows the highest elastic modulus and hardness of 101 GPa and 7.4GPa, respectively. Transmission electron microscopy reveals that nanocrystals form within the nanoglasses during compaction. Higher nanocrystal density correlates with higher nanoparticle crystallization enthalpy, an increase in plasticity, and a decrease in yield strength. Plastic strain of 5.0%, yield strength of 3.8GPa, and ultimate compressive strength of 2.7–3.8GPa were achieved. Here we show that the compaction of colloidal metallic glass nanoparticles results in robust bulk samples, with mechanical properties similar to that of other iron-based bulk metallic glasses.

36 MATERIALS SCIENCE↗

Multifunctional entinostat enhances the mechanical robustness and efficiency of flexible perovskite solar cells and minimodules

Flexible perovskite solar cells (F-PSCs), prized for their nature of soft and high power-weight compatibility, have attracted intensive attention. However, inferior buried perovskite-substrate interfaces due to low interfacial adhesion between perovskites and substrates and large deformation of flexible substrates have greatly limited the performance of F-PSCs. Here, we add organic molecule Entinostat (ET) into hole extraction material Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) to enhance the adhesion at the perovskite/substrate interface using the interactions of ET with perovskites, PTAA and indium tin oxide (ITO) through its multiple function groups. Meanwhile, ET added into perovskites reduces the voids at the bottom perovskite film, due to its capability to tune the crystallization of perovskites by forming adduct with lead. Consequently, the inverted small area F-PSCs achieved an efficiency of 23.4%. The flexible perovskite minimodule with an area of 9 cm 2 achieved an aperture efficiency of ~19.0% certified by National Renewable Energy Laboratory. Furthermore, the optimized unencapsulated flexible minimodule retained 84% of the initial efficiency after 5000 bending cycles and retained 90% of the initial PCE (T90) after light soaking for >750 hours.

14 SOLAR ENERGY↗

Real-Time X-Ray Transmission Microscopy of Solidifying Al-In Alloys

Real-time observations of transparent analog materials have provided insight, yet the results of these observations are not necessarily representative of opaque metallic systems. In order to study the detailed dynamics of the solidification process, we develop the technologies needed for real-time X ray microscopy of solidifying metallic systems, which has not previously been feasible with the necessary resolution, speed, and contrast. In initial studies of Al-In monotectic alloys unidirectionally solidified in an X-ray transparent furnace, in situ records of the evolution of interface morphologies, interfacial solute accumulation, and formation of the monotectic droplets were obtained for the first time: A radiomicrograph of Al-30In grown during aircraft parabolic maneuvers is presented, showing the volumetric phase distribution in this specimen. The benefits of using X-ray microscopy for postsolidification metallography include ease of specimen preparation, increased sensitivity, and three-dimensional analysis of phase distribution. Imaging of the solute boundary layer revealed that the isoconcentration lines are not parallel (as is often assumed) to the growth interface. Striations in the solidified crystal did not accurately decorate the interface position and shape. The monotectic composition alloy under some conditions grew in an uncoupled manner.

Curreri, Peter A.↗

Toward Optimum Scale and TBC Adhesion on Single Crystal Superalloys

Single crystal superalloys exhibit excellent cyclic oxidation resistance if their sulfur content is reduced from typical impurity levels of approximately 5 ppmw to below 0.5 ppmw. Excellent alumina scale adhesion was documented for PWA 1480 and PWA 1484 without yttrium additions. Hydrogen annealing produced effective desulfurization of PWA 1480 to less than 0.2 ppmw and was also used to achieve controlled intermediate levels. The direct relationship between cyclic oxidation behavior and sulfur content was shown. An adhesion criterion was proposed based on the total amount of sulfur available for interfacial segregation, e.g., less than or equal to 0.2 ppmw S will maximize adhesion for a 1 mm thick sample. PWA 1484, melt desulfurized to 0.3 ppmw S, also exhibited excellent cyclic oxidation resistance and encouraging TBC lives (10 mils of 8YSZ, plasma sprayed without a bond coat) in 1100 C cyclic oxidation tests.

Smialek, James L.↗

Catalytically mediated epitaxy of 3D semiconductors on van der Waals substrates

The formation of well-controlled interfaces between materials of different structure and bonding is a key requirement when developing new devices and functionalities. Of particular importance are epitaxial or low defect density interfaces between two-dimensional materials and three-dimensional semiconductors or metals, where an interfacial structure influences electrical conductivity in field effect and optoelectronic devices, charge transfer for spintronics and catalysis, and proximity-induced superconductivity. Epitaxy and hence well-defined interfacial structure has been demonstrated for several metals on van der Waals-bonded substrates. Semiconductor epitaxy on such substrates has been harder to control, for example during chemical vapor deposition of Si and Ge on graphene. Here, we demonstrate a catalytically mediated het-eroepitaxy approach to achieve epitaxial growth of three-dimensional semiconductors such as Ge and Si on van der Waals-bonded materials such as graphene and hexagonal boron nitride. Epitaxy is "transferred" from the substrate to semiconductor nanocrystals via solid metal nano-crystals that readily align on the substrate and catalyze the formation of aligned nuclei of the semiconductor. In situ transmission electron microscopy allows us to elucidate the reaction pathway for this process and to show that solid metal nanocrystals can catalyze semiconductor growth at a significantly lower temperature than direct chemical vapor deposition or deposition mediated by liquid catalyst droplets. We discuss Ge and Si growth as a model system to explore the details of such hetero-interfacing and its applicability to a broader range of materials.

36 MATERIALS SCIENCE↗