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At least 415 records · Page 23

Micro Crystalline Bamboo Cellulose Based Seaweed Biodegradable Composite Films for Sustainable Packaging Material

This study is aimed to fabricate and characterize the seaweed- biodegradable films incorporated with varying concentrations of microcrystalline cellulose (MCC) which was extracted from two bamboo sources: Schizostachyum brachycladum (BLMCC) and Gigantochloa scortechinii (BSMCC). Pure biodegradable seaweed film was directly fabricated from red seaweed (Kappaphycus alvarezii). In this demonstrated work, commercial MCC (CMCC), BLMCC and BSMCC were used to reinforce the pure seaweed bio-degradable film at different loading concentrations (0, 1, 3, 5, 7, 10 and 15%) based on the dried-weight of seaweed, for packaging applications. There was substantial improvement in the tensile strength and contact angle values while reduction in the water vapor permeability and elongation at break values with the incorporation of the CMCC, BLMCC and BSMCC into the seaweed pure film matrix, which is highly desirable for the packaging material in the current scenario. The morphology of the fabricated films confirmed that there was good dispersion of the 7% of CMCC, 5% of BLMCC and 3% of BSMCC in the pure seaweed films, which resulted in the enhanced mechanical properties. So far, this is the first report on the microcrystalline cellulose based seaweed films with excellent mechanical properties, which makes them suitable for packaging application. The demonstrated work proved that both BSMCC and BLMCC based seaweed composite films have the huge potential to be used as biodegradable packaging material for wide range of applications. Graphical Abstract: .

36 MATERIALS SCIENCE↗

Variation of the Passive Film on Compositionally Concentrated Dual-Phase Al 0.3 Cr 0.5 Fe 2 Mn 0.25 Mo 0.15 Ni 1.5 Ti 0.3 and Implications for Corrosion

The passive film on a dual-phase Al 0.3 Cr 0.5 Fe 2 Mn 0.25 Mo 0.15 Ni 1.5 Ti 0.3 FCC + Heusler (L2 1 ) compositionally concentrated alloy formed during extended exposure to an applied potential in the passive range in dilute chloride solution was characterized. Each phase, with its own distinct composition of passivating elements, formed unique passive films separated by a heterophase interface. High-resolution, surface sensitive characterization enabled chemical analysis of the passive film formed over individual phases. The film formed over the L2 1 phase had a higher concentration of Al, Ni, and Ti, while the film formed over FCC phase was of similar thickness but contained comparatively higher Cr, Fe, and Mo concentrations, consistent with the differences in bulk microstructure composition. The passive film was continuous across phase boundaries and the distribution of passivating elements (Al, Cr, and Ti) indicated both phases were independently passivated. Spatially resolved analysis of the surface chemistry of the dual-phase CCA revealed that the cation with the highest composition in passive film formed on the FCC phase was Cr (52.4 at. pct) and for the L2 1 phase was Ti (53.1 at. pct) despite the bulk concentration of each element being below 20 at. pct in their respective phases. Al, Cr, and Ti were enriched in both phases within the passive film relative to their respective bulk compositions. In parallel studies, single-phase alloys with compositions representative of the FCC and L2 1 phases were synthesized to evaluate the corrosion behavior of each phase in isolation. The corrosion behavior of the dual-phase alloy showed passivity evidenced by a pitting potential of 0.615 V SCE in 0.01 M NaCl. The pitting potential and other electrochemical parameters suggested a combination of behaviors of both single-phase samples, suggesting that the global corrosion behavior may be represented by a composite theory applied to phases, their area fractions, and interphase length. However, the interphase in the dual-phase CCA was a local corrosion initiation site and may limit localized corrosion protectiveness. The alloy design implications for optimization of second phase structure and morphology are discussed.

36 MATERIALS SCIENCE↗

Kinetics and evolution of solid-state metal dealloying in thin films with multimodal analysis

Thin-film solid-state metal dealloying (thin-film SSMD) is an emerging technique that uses self-organization to design nanostructured thin films. The resulting 3D bicontinuous nanostructures are promising for a wide range of applications, such as catalysis and energy storage. In this work, we prepared thin films by SSMD using Ti-Cu as the parent alloy and Mg as the solvent. Using a multimodal approach, we combined synchrotron X-ray spectroscopy, diffraction, and high-resolution electron-based spectroscopy and imaging to study their morphological, structural, and chemical evolution. The processing-structure relationship was analyzed as a function of parent alloy composition and dealloying temperature and time. Morphological transitions from globular, to lamellar, to bicontinuous structures, in conjunction with a ligament size evolution, were identified as functions of the parent alloy composition. The dealloying rate increased with increasing concentration of interdiffusing elements (dissolving component) in the parent alloy. The parting limit, a dealloying compositional threshold, was systematically analyzed and determined to be 30%–40%. The order of crystalline phase formation is CuMg 2 , Cu 2 Mg, and Ti; the Ti phase first shows self-reorganization during dealloying, separate from the crystallization process. The coarsening in thin-film SSMD was identified and not entirely self-similar; in addition to the increase of ligament size over time, the formation of larger globular ligaments were also observed. This work furthers our fundamental understanding of thin-film SSMD and nanostructured thin-film design, where the thermodynamic and kinetic effects differ from the bulk counterparts. The fact that dealloying and diffusion outpaces the crystallization and new phase formation also offers opportunities to utilize thin-film SSMD in certain alloy systems in which deleterious intermetallic phases need to be suppressed, that may not be possible in the bulk geometry.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Formation and degradation mechanism of methylammonium lead iodide perovskite thin film fabricated by electrospray technique

Electrospray deposition technique has been reported previously for fabricating effective and stable perovskite thin film, leading to efficient perovskite solar cells. Here, in this work, a comprehensive investigation of the formation mechanism of methylammonium lead iodide perovskite (CH 3 NH 3 PbI 3 ) film by electrospray technique is demonstrated and compared to the formation mechanism through the conventional spin coating technique. In the electrospray process, charged MAI nanoparticles are gradually introduced onto the PbI 2 film, intercalating within the PbI 2 structure to produce the perovskite film. In contrast, the spin-coating method involves supplying the MAI solution in bulk, leading to perovskite crystal formation through the dissolution of the PbI 2 layer by the MAI solution, followed by recrystallization into perovskite oriented in the [110] direction, 30° inclined to the substrate. The impact of charge and the electric field on the formation of perovskite film using the electrospray is explored. Furthermore, the intrinsic stability of perovskite films is monitored in real-time in a highly humid environment (≥80 % relative humidity (RH)) using in-situ Grazing Incidence Wide Angle X-ray Scattering (GIWAXS), and a degradation mechanism is proposed to enhance the durability of the perovskite-based devices. The study further delves into the comparison of the stability of electrosprayed and spin-coated perovskite film, and the impact of humidity level and the presence of a hole-transporting layer on the stability of the perovskite layer. Overall, this work provides a detailed understanding of the formation and humidity-induced degradation mechanism of electrosprayed perovskite films, offering insights that can extend to various applications of perovskite materials.

14 SOLAR ENERGY↗

Superconducting magnesium diboride films for levitation of laser targets

Inertial confinement fusion targets would benefit from being levitated inside hohlraums to avoid capsule support-related implosion perturbations. Levitation inside a magnetic trap requires coating the capsule with a thin film that is superconducting at 20 K. Such non-epitaxial film growth on non-planar substrates is challenging. Here, we study Mg vapor annealing and solid-phase reactive inter-diffusion methods to form superconducting magnesium diboride (MgB 2 ) films on different planar and spherical carbon substrates, evaluating glassy carbon, polycrystalline diamond made by chemical vapor deposition, and carbon deposited by magnetron sputtering of graphite targets. Thin films of B and Mg are produced by magnetron sputtering onto stationary planar or rolling spherical substrates and annealed at either 600 or 850 °C in Mg vapor. The films are characterized by a combination of high-energy ion scattering, electron microscopy, and magnetometry. Results show that the critical superconducting temperature of resultant films depends on film microstructure and oxygen impurity content. The formation of MgB 2 films is also strongly substrate dependent, even in this case of non-epitaxial growth. Important factors to consider are oxygen outgassing of the substrate during thermal processing, substrate surface roughness, and the matching of thermal expansion coefficients of different layers in the multilayer structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Stretching and Bending Moduli of Bilayer Films Inferred from Wrinkle Patterns

Wrinkling patterns were used to investigate the mechanical properties of thin poly­(styrene) (PS)/poly­(methyl methacrylate) (PMMA) and PS/gold (Au) bilayer films. Films were floated on water with a water drop on the surface to induce wrinkling. The thicknesses and thickness ratios of the films were varied over a broad range. The PS/PMMA bilayer was chosen to provide a contrast in wetting properties, with equilibrium contact angles of θPMMA = 68° and θPS = 88° with water. The PS/Au bilayer was chosen to provide a large contrast in Young’s moduli, E Au = 72 GPa and E PS = 3.4 GPa. The stretching (Y) and bending (B) moduli of the bilayer films were obtained from measurements of the length and number of wrinkles in the wrinkle patterns. The experimentally derived values of Y and B were in reasonable agreement with the values computed from the bulk Young’s moduli and the thicknesses of the two components in the bilayer. The values of Y and B did not depend on which face of the film was exposed to the water droplet or bath when the capillary stresses were considered. Thus, finite size effects from the film thicknesses were unimportant over the range of thicknesses studied, and no relative displacement of the films was found, with the films remaining well-bonded even with deformation associated with wrinkling.

Chang, Jooyoung↗

Defect Annihilation in the Directed Self-Assembly of Block Copolymers in Films with Increasing Thickness.

We investigate directed self-assembly (DSA), with 3x density multiplication, of symmetric polystyrene-block-poly(methyl methacrylate) (L-0 = 28 nm) with increasing film thicknesses and reveal a thickness limit above which the defect annihilation mechanism is different than in thinner films. Block copolymer films of increasing thickness underwent DSA on a macroscopic chemical pattern under optimum geometrical and chemical conditions. Scanning electron microscopy and grazing-incidence small-angle X-ray scattering (GISAXS) were used to characterize the long-range ordering and buried structures as a function of film thickness and thermal annealing time. Rotational GISAXS measurements revealed a critical thickness of similar to 3L(0,) below which defect annihilation is cooperative across the film depth and above which it is faster at the free surface than in the film's interior. In the latter case, defects can persist in the film's interior despite perfect assembly and registration at the free surface of the film.

Chen, Xuanxuan↗

Tailoring low energy electron absorption via surface nano-engineering of cesiated chromium films

Here, we demonstrate that improved low energy electron absorption is achieved by suppressing the crystallinity of chromium thin-films grown on W[110], which points to a promising route for achieving highly efficient thermionic energy converters. Using low energy electron microscopy (LEEM) and in situ film growth, we show that substrate temperature control permits well-controlled fabrication of either epitaxial Cr[110] films or nanocrystalline Cr layers. We show that the work function of cesium saturated nanocrystalline Cr thin-films is ~0.20 eV lower than that of epitaxial Cr[110] films. Our LEEM measurements of absorbed and reflected currents as a function of electron energy demonstrate that nanocrystallinity of cesiated chromium films results in 96% electron absorption in the range up to 1 eV above the work function, compared to just 79% absorption in cesiated crystalline Cr[110] films. These results point to metal films with suppressed crystallinity as an economical and scalable means to synthesize nanoengineered surfaces with optimized properties for next generation anode materials in high performance thermionic energy converters.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Investigation of UV, ns-laser damage resistance of hafnia films produced by electron beam evaporation and ion beam sputtering deposition methods

Laser-induced damage in coating materials with a high index of refraction, such as hafnia, limits the performance of high power and high energy laser systems. Understanding the underlying physics responsible for laser damage holds the key for developing damage-resistant optical films. Previous studies have reported a substantial difference in laser damage onset for hafnia films produced by different deposition methods, yet the underlying mechanisms for the observed difference remain elusive. We combined laser damage testing with analytical characterizations and theoretical simulations to investigate the response of hafnia films produced by electron (e-) beam evaporation vs ion beam sputtering (IBS) methods upon UV ns-laser exposure. We found that e-beam produced hafnia films were overall more damage resistant; in addition, we observed a polarization anisotropy associated with the onset of damage in the e-beam films, while this effect was absent in the latter films. The observed differences can be attributed to the stark contrast in the pressure inside the pores inherent in both films. The high pressure inside the IBS-induced nanobubbles has been shown to reduce the threshold for laser-induced plasma breakdown leading to film damage. The polarization effects in the e-beam coatings can be related to the asymmetric electric field intensification induced by the columnar void structure. Our findings provide a fundamental basis for developing strategies to produce laser damage-resistant coatings for UV pulsed laser applications.

36 MATERIALS SCIENCE↗

Direct measurement of microwave loss in Nb films for superconducting qubits

Niobium films are a key component in modern two-dimensional superconducting qubits, yet their contribution to the total qubit decay rate is not fully understood. The presence of different layers of materials and interfaces makes it difficult to identify the dominant loss channels in present two-dimensional qubit designs. In this paper, we present the study that directly correlates measurements of RF losses in such films to material parameters by investigating a high-power impulse magnetron sputtered (HiPIMS) film atop a three-dimensional niobium superconducting radio frequency (SRF) resonator. By using a 3D SRF structure, we are able to isolate the niobium film loss from other contributions. Our findings indicate that microwave dissipation in the HiPIMS-prepared niobium films, within the quantum regime, resembles that of record-high intrinsic quality factor of bulk niobium SRF cavities, with lifetimes extending into seconds. Microstructure and impurity level of the niobium film do not significantly affect the losses. These results set the scale of microwave losses in niobium films and show that niobium losses do not dominate the observed coherence times in present two-dimensional superconducting qubit designs, instead highlighting the dominant role of the dielectric oxide in limiting the performance. We can also set a bound for when niobium film losses will become a limitation for qubit lifetimes.

Abdisatarov, B.↗

Resistive Switching in SrFeO2.5/Nb:SrTiO3 Heterostructures with Growth-Controlled Film Orientation

Resistive switching, a behavior found in many oxide materials, has the potential to enable emerging computer hardware technologies and architectures. We present resistive switching devices fabricated from epitaxial brownmillerite SrFeO2.5 films with two distinct film orientations, wherein facile oxygen ion diffusion planes are aligned parallel (in-plane) and perpendicular (out-of-plane) with the electrodes. SrFeO2.5 films were grown on (001) oriented Nb:SrTiO3 to enable high-quality interfaces and future integration with Si CMOS technologies. Post-growth vacuum annealing and growth pressure were used to control film orientations, as confirmed by transmission electron microscopy and x-ray diffraction measurements. Films grown with diffusion planes oriented in-plane had oxygen-rich, perovskite-like nanodomains spread throughout the film, and fabricated devices exhibited worse switching consistency and more stochasticity. In contrast, films grown with diffusion planes oriented out-of-plane had a more uniform oxygen-rich perovskite interfacial layer above the bottom electrode, and devices built from this film orientation showed significant statistical improvements in switching voltages and cycling consistency.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Optimized oxygen deprived low temperature sputtered WO3 thin films for crystalline structures

In this work, we report a detailed analysis on the effects of processing parameters for sputtered tungsten trioxide (WO 3 ) thin nanoscale films on their structural, vibrational and electrical properties. The research aims to understand the fundamental aspects of WO3 sputtering at relatively low temperatures and in an oxygen deprived environment targeting applications of temperature and oxygen sensitive substrates. Structural analysis indicates that films deposited at room temperature, or substrate temperatures at or below 400 degrees C with low oxygen partial pressure are amorphous. Furthermore, crystallization of the films was observed with distinct Raman peaks when the films were annealed at 300 degrees C or above using rapid thermal annealing for 10 min. Films revealed monoclinic phases of WO 3 with the presence of W-O-W stretching, bending and lattice vibrational modes in the Raman spectra. Interestingly, a change of transport behavior from insulating to semiconducting was observed for as deposited films on post annealing. Annealed films revealed stoichiometric WO 3 phases with no external defects detected. The present study adopts a route to intercalate WO 3 in a variety of applications from electrochromic coloration to a nanocrystalline thin film for electronic devices sensitive to higher temperatures and gas flow in the sputtering system.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Discovery and adaptation of microbes that degrade oxidized low-density polyethylene films

There is a growing interest in developing a methodology for effectively cleaving carbon–carbon (C–C) bonds in polymer backbones through bioconversion processes that utilize microorganisms and their enzymes. This upsurge of interest is driven by the goal of achieving a circular economy. Polyolefin post-consumer plastics are a substantial source of carbon, but the recycling potential is severely limited. Upcycling routes are needed for converting polyolefin post-consumer plastics into value-added products while concurrently mitigating adverse environmental effects. These materials contain carbon-based chemicals that can, in principle, serve as the feedstock for microbial metabolism. Some microbes have been reported to grow on polyolefin plastics, but the rate of biodegradation is insufficient for industrial processes. In this study, low-density polyethylene (LDPE) films were subjected to two mild ozone-based oxidation treatments, which facilitated biodegradation. The degree of oxidation was determined by Fourier transform infrared spectroscopy via analysis of the carbonyl index (1,710/1,460 cm −1 ), which ranged from 0.3 to 2.0, and also via analysis of the carboxylic acid content. Following oxidation of the films, studies were conducted to investigate the ability of a panel of polyvinyl alcohol-degrading microbes to degrade the oxidized films. A defined minimal medium was used to cultivate and assess microbial growth on the oxidized films. Following 45 days of cultivation, the most effective strains were further cultivated up to three additional generations on the oxidized film substrates to improve their ability to degrade the oxidized LDPE films. After these enrichments, we identified a strain from the third generation of Pseudomonas sp. Rh926 that exhibited significant cell growth and reduced the oxidized LDPE film mass by 25% in 30 days, demonstrating an enhanced capacity for degrading the oxidized LDPE films.

Adaptation↗

Modification of spin-ice physics in Ho 2 Ti 2 O 7 thin films

We present an extensive study on the effect of substrate orientation, strain, stoichiometry, and defects on spin-ice physics in Ho 2 Ti 2 O 7 thin films grown onto yttria-stabilized-zirconia substrates. We find that growth in different orientations produces different strain states in the films. All films exhibit similar c -axis lattice parameters for their relaxed portions, which are consistently larger than the bulk value of 10.1 Å. Transmission electron microscopy reveals antisite disorder and growth defects to be present in the films, but evidence of stuffing is not observed. The amount of disorder depends on the growth orientation, with the (110) film showing the least. Magnetization measurements at 1.8 K show the expected magnetic anisotropy and saturation magnetization values associated with a spin ice for all orientations; shape anisotropy is apparent when comparing in- and out-of-plane directions. Significantly, only the (110)-oriented films display the hallmark spin-ice plateau state in magnetization, albeit less well defined compared to the plateau observed in a single crystal. Neutron-scattering maps on the more disordered (111)-oriented films show the Q=0 phase previously observed in bulk materials, but the Q=X phase giving the plateau state remains elusive. We conclude that the spin-ice physics in thin films is modified by defects and strain, leading to a reduction in the temperature at which correlations drive the system into the spin-ice state.

36 MATERIALS SCIENCE↗

How Excitation Conditions Alter the Afterglow Characteristics of CsI:Tl,Sm Microcolumnar Films

Combining high light output with the microcolumnar structure, the CsI:Tl films significantly reduce the need for painful tradeoff between thickness (hence, stopping power) and spatial resolution. But both films and monocrystals share two important deficiencies that hinder their use in many high-speed imaging and computed tomography applications: a persistent afterglow and hysteresis. These properties receive the primary attention of this investigation. In our earlier work, we reported that codoping with Sm 2+ brings about a significant reduction in the afterglow of CsI:Tl. Here, focusing on the microcolumnar films, we examine this afterglow-suppressive effect over a wide range of exposure times, from milliseconds to seconds, and at temperatures between 0 °C and 60 °C. Our measurements reveal well-defined dependences on both parameters. At room temperature (20 °C), defined as the normal operating condition, a 10-ms X-ray pulse leaves an afterglow from the standard (Sm-free) CsI:Tl of about 1% at 2 ms after the end of the pulse, changing little as a function of pulselength. Doping with Sm 2+ , however, reduces that afterglow by at least an order of magnitude, although somewhat less so after longer (100 and 1000 ms) pulses. When we change the temperature, however, we find markedly different behavior. Here, we find that a temperature increase of only 60°, without changing the pulselength, cuts the afterglow of standard CsI:Tl films by a factor of 20. However, films of codoped CsI:Tl,Sm, whose afterglow has already been suppressed by the presence of Sm 2+ , show much less change as a function of either temperature or pulse duration. It is the presence of Sm 2+ that makes the biggest difference. As for hysteresis, we again see an improvement, with the performance of the codoped CsI:Tl,Sm films bettering that of the standard (Sm-free) films. After an exposure of 300 mR, the change in light output falls to within 1% of the original after 1 min, whereas standard CsI:Tl films require 30 min to reach the same level.

42 ENGINEERING↗

Dynamic asymmetric strain imprinted into substrates by an oxide thin film

In film-substrate systems, the substrate role is often considered to be limited to providing static mechanical constraints. Dynamic film-substrate interactions when a structural change in the film modifies the substrate are generally disregarded. Here, using combined x-ray and electron microscopies, we observed that an electrically induced filament in a vanadium dioxide film created strong asymmetric strain in an underlying sapphire substrate. This asymmetric substrate strain fed back into the film and defined the filament expansion direction, revealing the importance of film-substrate dynamic interactions in determining film functionality. Furthermore, the strain imprint propagated at least tens of micrometers deep into the substrate, exceeding the film thickness by more than 200-fold, potentially enabling substrate functionalization as an active mechanical coupling media in three-dimensional integrated microelectronic architectures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Factors Controlling Electrochemistry-Induced Deposition of a Zeolitic Imidazolate Framework-8 Film on Underlying Substrates

This paper discusses factors controlling electrochemistry-induced deposition of a zeolitic imidazolate framework-8 (ZIF-8) film on a planar substrate that is placed under an electrode. This method, which was recently demonstrated by us [T. Ito, et al. Cryst. Growth Des., 23, 6369 (2023)], provides a simple means to form a ZIF-8 film having lateral dimensions replicating those of a working electrode on an underlying substrate. We reported the effects of applied cathodic potential, electrode–substrate distance, and deposition time on the film formation, and proposed a mechanism involving cathodic base generation at a working electrode that promoted ligand deprotonation to form intermediate species, followed by their diffusion toward an underlying substrate. Here, we discuss details on the deposition mechanism by investigating the influences of other factors on the film deposition. We have investigated the effects of precursor concentration on film formation, and clarified that O 2 is a probase, rather than H 2 O. We have also shown the influences of substrate surface properties controlled by self-assembled monolayers on film thickness and morphology. Most notably, we successfully demonstrated the formation of microscale ZIF-8 films using an ultramicroelectrode, revealing the applicability of the electrochemistry-induced method for micropatterned film deposition on an underlying substrate.

36 MATERIALS SCIENCE↗