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At least 577 records · Page 32

Impact of Fermentation-Derived Substrates on Hydrogen Production in Zero-Gap Microbial Electrolysis Cells

Zero-gap microbial electrolysis cells (MECs) represent a promising platform for hydrogen production from liquid waste streams due to reduced interelectrode spacing that lowers internal resistance and enhances mass transport. However, the performance and stability of zero-gap MECs treating chemically complex feedstocks remain insufficiently characterized. Here, we operated zero-gap MECs with real, unamended, corn stover dark fermentation effluent containing a wide range of organic substrates. The MECs fed fermentation effluent achieved a maximum current density of 24 A/m2 (15+-6 A/m2 over the cycle) and a hydrogen production rate of 75 L/L-d (42+-19 L/L-d over the cycle). The substrates were consumed at different rates, indicating substrate-selective utilization by the anodic microbial community. Acetate supported high and stable current generation, whereas ethanol, formate, lactate, and amino acids induced varying degrees of inhibition depending on their concentration. Residual sugars caused pronounced current fluctuations, consistent with ongoing fermentation and local pH changes. A diverse microbial community was crucial for efficiently utilizing complex organics and maximizing electrochemical performance. These results demonstrate how and to what extent substrate composition regulates zero-gap MEC performance and that microbial community and operational conditions can be leveraged to enhance performance. These novel findings provide practical guidance for achieving robust hydrogen recovery from chemically heterogeneous real liquid waste streams.

08 HYDROGEN↗

Effect of substrates on microstructure and mechanical properties of nano-eutectic 1080 steel produced by aluminothermic reaction

Nano-eutectic bulk 1080 carbon steel was prepared on glass and copper substrates by an aluminothermic reaction casting. The microstructure of the steel was analyzed by an optical microscope, transmission electron microscopy, an electron probe micro-analyzer, a scanning electron microscope and X-ray diffraction. Results show that the microstructure of the steel consisted of a little cementite and lamellar eutectic pearlite. Average lamellar spacing of the pearlite prepared on copper and glass substrates was about 230 nm and 219 nm, respectively. Volume fraction of the pearlite of the two steels was about 95%. Hardness of the steel was about 229 and 270 HV. Tensile strength was about 610 and 641 MPa and tensile elongation was about 15% and 8%. Compressive strength was about 1043 and 1144 MPa. Compared with the steel prepared on copper substrate, the steel prepared on glass substrate had smaller lamellar spacing of the pearlite phase and higher strength, and low ductility due to the smaller spacing. - Highlights: • 1080-carbon steels were successfully prepared by an aluminothermic reaction casting. • Lamellar spacing of the nanoeutetic pearlite is less than 250 nm. • The compressive strength of the steel is about 1144 MPa. • The tensile ductility of the steel is about 15%.

36 MATERIALS SCIENCE↗

Twin-assisted growth of nominally stable substrates underneath dewetted Au nanoparticles

By applying a simple and inexpensive thermal treatment, we synthesized supported gold-oxide nanostructures, which have potential applications to plasmonic devices and biosensors. The regrowth of nominally stable substrates under gold nanoparticles is associated with the appearance of preferential orientations of dewetted nanoparticles and the formation of atomically sharp interfacial monolayers. Steps present at the interfacial monolayer usually occur at defects including the intersection points of twin planes at the interface. They were related to the nucleation and immigration of the interfacial monolayers, prompting the substrate regrowth. Accordingly, we proposed the twin-assisted growth mechanism, which provides insight on the synthesis of gold-oxide nanostructures. - Highlights: • The twin-assisted growth mechanism is proposed for the abnormal regrowth of substrate underneath Au nanoparticles. • The substrate regrowth is related to the steps and ledges that are present at the Au–MgAl{sub 2}O{sub 4} interfacial monolayers. • Interfacial steps are detected at defects such as the intersecting points of twin planes at the interface.

36 MATERIALS SCIENCE↗

Transfer of microstructure pattern of CNTs onto flexible substrate using hot press technique for sensing applications

Graphical abstract: - Highlights: • Successfully transfer of microstructure patterned CNTs on PET substrate. • Demonstrate as resistor-based NH{sub 3} gas sensor in the sub-ppm range. • Excellent photodetector having instantaneous response and recovery characteristics. • An effective technique to grow and produce flexible electronic device. - Abstract: In this work, we report the successful and efficient transfer process of two- dimensional (2-D) vertically aligned carbon nanotubes (CNTs) onto polyethylene terephthalate (PET) substrate by hot pressing method with an aim to develop flexible sensor devices. Carbon nanotubes are synthesized by cold wall thermal chemical vapor deposition using patterned SiO{sub 2} substrate under low pressure. The height of the pattern of CNTs is controlled by reaction time. The entire growth and transfer process is carried out within 30 min. Strong adhesion between the nanotube and polyethylene terephthalate substrate was observed in the post-transferred case. Raman spectroscopy and scanning electron microscope (SEM) studies are used to analyze the microstructure of carbon nanotube film before and after hot pressing. This technique shows great potential for the fabrication of flexible sensing devices. We report for the first time, the application of patterned microstructure developed by this technique in the development of gas sensor and optoelectronic device. Surface resistive mode is used for detection of ammonia (NH{sub 3}) gas in the sub-ppm range. An impressive photoconducting response is also observed in the visible wavelength. The reproducibility of the sample was checked and the results indicate the possibility of use of carbon nanotube as gas sensor, photodetector, CCDs etc.

36 MATERIALS SCIENCE↗

Suspension chemistry and electrophoretic deposition of zirconia electrolyte on conducting and non-conducting substrates

Graphical abstract: - Highlights: • Stable suspension of yttria stabilized zirconia (YSZ) obtained in isopropanol medium. • Suspension chemistry and process parameters for electrophoretic deposition optimized. • Deposited film quality changed with iodine and water (dispersants) concentration. • Dense YSZ film (∼5 μm) fabricated onto non-conducting porous NiO-YSZ anode substrate. - Abstract: Suspensions of 8 mol% yttria stabilized zirconia (YSZ) particulates in isopropanol medium are prepared using acetylacetone, iodine and water as dispersants. The effect of dispersants concentration on suspension stability, particle size distribution, electrical conductivity and pH of the suspensions are studied in detail to optimize the suspension chemistry. Electrophoretic deposition (EPD) has been conducted to produce thin and dense YSZ electrolyte films. Deposition kinetics have been studied in depth and good quality films on conducting substrate are obtained at an applied voltage of 15 V for 3 min. YSZ films are also fabricated on non-conducting NiO-YSZ anode substrate using a steel plate on the reverse side of the substrate. Upon co-firing at 1400 °C for 6 h a dense YSZ film of thickness ∼5 μm is obtained. Such a half cell (anode + electrolyte) can be used to fabricate a solid oxide fuel cell on applying a suitable cathode layer.

36 MATERIALS SCIENCE↗

A simple approach for the synthesis of Ag-coated Ni@TiO{sub 2} nanocomposites as recyclable photocatalysts and SERS substrate to monitor catalytic degradation of dye molecules

Graphical abstract: - Highlights: • A simple approach was used to synthesize Ag-coated Ni@TiO{sub 2} nanocomposites. • The nanocomposites can be the convenient and effective SERS substrate. • The nanocomposites can be a self-cleaning SERS substrate. • The nanocomposites can monitor the catalytic degradation of dye molecules. - Abstract: In this work, we demonstrate an extremely simple and speedy approach to synthesis Ag-coated Ni@TiO{sub 2} nanocomposites, which can be a convenient and effective substrate for surface enhanced Raman spectroscopy (SERS) observation. Due to possessing the excellent magnetic properties and stable catalytic properties at room temperature, the nanocomposites can clean themselves by photocatalytic degradation of dye molecules under irradiation with UV light into inorganic small molecules for the self-cleaning SERS detection. Furthermore, the nanocomposites can be used as the SERS substrate for monitoring the catalytic degradation of dye molecules.

36 MATERIALS SCIENCE↗

Modulation of microstructure and optical properties of Mo-doped ZnO thin films by substrate temperature

Highlights: • Mo-doped ZnO films are obtained by sputtering at various substrate temperatures. • High-quality MZO thin films with good crystalline have been obtained at 200 °C. • Deposition temperature affects the amount of defects in the crystalline structure - Abstract: Mo-doped ZnO(MZO) films were deposited on Si (1 1 1) substrates by radio frequency sputtering at different substrate temperatures of 200, 300 and 400 °C. The effect of the substrate temperature on the structural and optical properties of the MZO films has been investigated. X-ray diffraction results reveal that all the films are polycrystalline with a hexagonal wurtzite structure with a preferential orientation according to the direction (0 0 2) plane. The crystallinity and surface morphologies of the films are strongly dependent on the growth temperature, which in turn exerts a great effect on microstructural and optical properties of the MZO films. The optical absorption measurements show high ultraviolet (UV) absorbance property of MZO with sharp and intense absorption band in this region and the optical band gap (E{sub g}) are 3.18, 3.22, 3.25 and 3.21 eV for the films deposited at room temperature, 200, 300 and 400 °C. The photoluminescence (PL) intensity of a strong broad violet–blue emission from MZO nanostructures with increasing deposited temperature was also observed. X-ray photoelectron spectroscopy (XPS) was employed to investigate the surface chemical composition of growth products.

36 MATERIALS SCIENCE↗

Substrate bias induced synthesis of flowered-like bunched carbon nanotube directly on bulk nickel

Highlights: • Flowered-like bunched MWCNTs have been synthesized by MW PECVD technique. • Effect of substrate bias on the properties of MWCNT has been studied. • Minimum E{sub T} = 1.9 V/μm with β = 4770 has been obtained in the film deposited at −350 V. - Abstract: This paper reports the effect of substrate bias on the multiwalled carbon nanotube (MWCNT) deposited on nickel foil by microwave plasma enhanced chemical vapor deposition technique. The MWCNTs have been characterized by the scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), Raman spectroscopy, field emission and current–voltage characteristic of the heterojunction diode. The SEM images exhibit unique hierarchical flowered-like bunched and conformally coated MWCNTs. Substrate bias induced ion bombardment helps in the enhancement of hydrocarbon dissociation and is responsible for flowered-like MWCNTs growth. The HRTEM micrographs show the base growth mechanism for MWCNTs. The value of turn on field for emission decreases from 5.5 to 1.9 V/μm and field enhancement factor increases from 927 to 4770, respectively, with the increase of substrate bias. The diode ideality factor of CNT/ n-Si heterojunction is evaluated as 2.4 and the on/off current ratio is found to be 7 at ±2 V, respectively.

36 MATERIALS SCIENCE↗

Effect of Ar ion-beam-assistance and substrate temperature on physical properties of Al-doped ZnO thin films deposited by RF magnetron sputtering

Highlights: • AZO and IAZO (303–473 K) films were grown by RF magnetron sputtering technique. • Ar ion-beam converts its kinetic energy as diffusion energy to the deposited atoms. • Structural evolution relies on diffusion energy imparted to the deposited atoms. • Surface texture densify under the aid of ion-beam and substrate temperature. - Abstract: In this study, pronounced effects of ion-beam-assistance and substrate temperature were revealed by exploring the physical properties of Al-doped ZnO thin films deposited by the RF magnetron sputtering technique. Herein, two measurable parameters, ion-beam discharge current (0.1 A) and substrate temperature (303–473 K) were adopted to regulate the structural changes in Al-doped ZnO films. Specifically, progressive structural changes were achieved based on the addition of Ar ion-beam during the film growth. From XRD analysis, we observed significant structural changes that provided an improvement in the film growth towards c-axis (002) plane. In addition, FESEM and AFM analyses demonstrated excellent surface features with the assisted Ar ion-beam. As a result of this process, we effectively modulated the binding energy of Zn 2p level. Finally, the structural investigation accurately demonstrated that the dependence of assisted ion-beam and substrate temperature linearly related to the superior visible transmittance and reduced band gap.

36 MATERIALS SCIENCE↗

Microstructural evolution, defect mitigation, and precipitation behavior in AA6061 via laser powder bed fusion with high-temperature substrate heating

Defects, particularly solidification cracking, remain persistent challenges in the laser powder bed fusion (LPBF) processing of AA6061 aluminum alloy. This study systematically investigates defect mitigation, microstructural evolution, and mechanical properties associated with high-temperature substrate preheating at 500 °C. Comprehensive microstructural analyses, including characterization of defects, grain structures, and precipitation behavior, were performed on samples in both as-built and T6 heat-treated states. Elevated preheating substantially reduced solidification cracking across a wide processing window, while demonstrating decreased crack sensitivity to laser parameters. Columnar cracks along the build direction were observed despite substrate preheating. Lack-of-fusion and keyhole porosity were effectively eliminated, though gas-induced microporosity persisted at higher powers. In-depth characterization of two distinct laser power and speed conditions confirmed the formation of micron-sized, non-coherent Mg 2 Si precipitates under heated substrate conditions, alongside α-AlFeCrMnSi intermetallic phases indicative of in-situ thermal effects during fabrication. Subsequent T6 heat treatment revealed the formation of fine, coherent needle-shaped β″ strengthening precipitates. Despite substantial differences in processing parameters, comparable mechanical properties were measured in the as-built samples (∼52 MPa yield strength, ∼130 MPa tensile strength), primarily due to reduced strain hardening effects and consistent precipitation characteristics. Meanwhile, the T6 heat treatment led to significant improvement in properties, enhancing yield strength by over 400%, aligning closely with the performance of conventional wrought AA6061-T6. These findings underscore that high-temperature substrate preheating offers an effective means to suppress cracks, control precipitation, and enhance mechanical performance in LPBF-processed AA6061.

36 MATERIALS SCIENCE↗

Chemical identity of carbon substrates drives differences in denitrification and N 2 O reduction within agricultural soils

Rates of nitrous oxide (N 2 O) production from agricultural soils are highly variable across space and time. Improving predictions of N 2 O emissions will require improving our understanding of the drivers of denitrification and the sources of variability in the rates of N 2 O production between soils and over time. While the amount of available carbon (C) is a known control on denitrification and N 2 O reduction, relatively little attention has been paid to the effect of the chemical identity of C substrates on rates of denitrification and N 2 O reduction. We investigated the effects of twelve different C-substrate additions on the production and reduction of N 2 O in five soils taken from two distinct agricultural locations in Michigan under multiple land uses. We provided additions of glucose, cellulose, N-acetyl-glucosamine, chitin, amino acids, protein, vanillyl alcohol, lignin, citrate, succinate, methanol, and water in laboratory denitrification potential assays to determine the effects of denitrifier C preference on denitrification rates. We found that amino acids, protein, and organic acids stimulated the greatest rates of denitrification potential across all land uses. Similarly, we found these same substrates caused the most N 2 O reduction, resulting in the lowest net concentrations of N 2 O. Soils from agricultural rotations without cover crops had overall lower rates of denitrifier activity, leading to less net N 2 O production compared to soils from other land uses. In general, C-utilization patterns were similar among all soils, and C-substrate identity had a much stronger effect than land use. Here, we demonstrate that the chemical identity of available C gives rise to wide variability in rates of denitrification and N 2 O reduction.

60 APPLIED LIFE SCIENCES↗

Reversal of Catalytic Material Substrate Selectivity through Partitioning of Polymers in Hierarchically Ordered Virus-like Particle Frameworks

Control over the selectivity of catalytic materials is a topic of growing interest. Virus-like particle (VLP) based materials such as protein macromolecular frameworks (PMFs) are promising for catalytic applications due to their ease of assembly, modular ability to encapsulate a variety of enzymes, and ease of separation from a reaction mixture. Here we demonstrate the reversal of the initially negative material charge through the titration of a positively charged polymer into the material, causing the reversal of guest molecule uptake and enzymatic activity of PMFs. The charge-inverse material partitions a charged enzyme substrate to concentrate the substrate near an enzyme incorporated within the material, generating up to 5.9-fold increases in enzyme activity toward the partitioned substrate over the excluded substrate. Here we also show that the polymer distributes heterogeneously through the material up to a point of saturation and the effects of guest macromolecules on the lattice parameters of PMFs.

36 MATERIALS SCIENCE↗

Roughness of Ti Substrates for Control of the Preferred Orientation of TiO 2 Nanotube Arrays as a New Orientation Factor

We report the surface roughness of a Ti substrate as a critical factor for controlling the degree of the preferred orientation of anatase TiO2 nanotube arrays (NTAs) which are synthesized by anodization and a subsequent annealing process. The degree of the preferred orientation to the (004) plane of the anatase crystal structure has a strong dependency on the root-mean-square roughness (Sq) of the initial Ti substrate when the roughness-controlled substrates are anodized in an ethylene glycol-based electrolyte containing ~2 wt % of water. Highly preferred oriented NTAs were obtained from low-Sq (<10 nm) substrates, which were accompanied by uniform pore distribution and low concentration of hydroxyl ions in as-anodized amorphous NTAs. The mechanism of the preferred oriented crystallization of nanometer-scaled tube walls is explained considering the microscopic geometrical uniformity of the oxide barrier and nanopores at the early stage of anodization, which affected the local electric field and thus the insertion of the hydroxyl group into the amorphous TiO2 tube walls.

14 SOLAR ENERGY↗

Insights from designing an artificial cascade catalysis system using principles from substrate channeling in enzymes

Generalizing the key requirements of highly-selective, multi-step chemical conversions involving spatially separated reaction centers remains one of the grand challenges of chemistry. Much work towards this effort has focused on decomposing multi-step conversions into their constituent reactions, whose intermediates are successively upgraded in a chemical cascade via diffusion from center to center. This approach for synthesizing more complex molecules takes its cues from biochemical networks, where near-unit conversion of even complex carbohydrates is achieved by upgrading chemical precursors via enzymatic cascades. In this computational study we examine a simple cascade involving coupled Ag and Cu catalysts that sequentially converts CO2 to CO and then CO2 and CO to reduced products, generically named CO2Product and COProduct. The system architecture is inspired by the phenomenon of biological substrate channeling, and components are examined to evaluate their effects on conversion efficiency in the cascade. Aside from a substrate channel linking two reaction centers, we find efficient cascades must also incorporate directional substrate diffusion, compartmentalization of the reaction centers, and proper timing of substrate arrival at the active center. We make explicit linkages between these requirements and chemical conversion in known biological systems, revealing additional control elements that could be incorporated.

CO 2 reduction↗

Impact of substrate temperature on the structural and optical properties of strain-balanced InAs/InAsSb type-II superlattices grown by molecular beam epitaxy

Molecular beam epitaxial growth of strain-balanced InAs/InAs{sub 1-x}Sb{sub x} type-II superlattices on GaSb substrates has been investigated for substrate temperatures from 400 Degree-Sign C to 450 Degree-Sign C. The Sb composition is found to vary linearly with substrate temperature at constant V/III ratios. For samples grown at the optimized substrate temperature (410 Degree-Sign C), superlattice zero-order peak full-width at half-maximums are routinely less than 25 arc sec using high-resolution X-ray diffraction. Cross-sectional transmission electron microscopy images show the absence of any visible defects. Strong photoluminescence covers a wavelength range from 5.5 to 13 {mu}m at 12 K. Photoluminescence linewidth simulations show satisfactory agreement with experiments.

36 MATERIALS SCIENCE↗

Structural and optical properties of Ag-doped copper oxide thin films on polyethylene napthalate substrate prepared by low temperature microwave annealing

Silver doped cupric oxide thin films are prepared on polyethylene naphthalate (flexible polymer) substrates. Thin films Ag-doped CuO are deposited on the substrate by co-sputtering followed by microwave assisted oxidation of the metal films. The low temperature tolerance of the polymer substrates led to the search for innovative low temperature processing techniques. Cupric oxide is a p-type semiconductor with an indirect band gap and is used as selective absorption layer solar cells. X-ray diffraction identifies the CuO phases. Rutherford backscattering spectrometry measurements confirm the stoichiometry of each copper oxide formed. The surface morphology is determined by atomic force microscopy. The microstructural properties such as crystallite size and the microstrain for (-111) and (111) planes are calculated and discussed. Incorporation of Ag led to the lowering of band gap in CuO. Consequently, it is determined that Ag addition has a strong effect on the structural, morphological, surface, and optical properties of CuO grown on flexible substrates by microwave annealing. Tauc's plot is used to determine the optical band gap of CuO and Ag doped CuO films. The values of the indirect and direct band gap for CuO are found to be 2.02 eV and 3.19 eV, respectively.

36 MATERIALS SCIENCE↗

In situ study of the role of substrate temperature during atomic layer deposition of HfO{sub 2} on InP

The dependence of the “self cleaning” effect of the substrate oxides on substrate temperature during atomic layer deposition (ALD) of HfO{sub 2} on various chemically treated and native oxide InP (100) substrates is investigated using in situ X-ray photoelectron spectroscopy. The removal of In-oxide is found to be more efficient at higher ALD temperatures. The P oxidation states on native oxide and acid etched samples are seen to change, with the total P-oxide concentration remaining constant, after 10 cycles of ALD HfO{sub 2} at different temperatures. An (NH{sub 4}){sub 2} S treatment is seen to effectively remove native oxides and passivate the InP surfaces independent of substrate temperature studied (200 °C, 250 °C and 300 °C) before and after the ALD process. Density functional theory modeling provides insight into the mechanism of the changes in the P-oxide chemical states.

36 MATERIALS SCIENCE↗

Growth mechanism and microstructure of low defect density InN (0001) In-face thin films on Si (111) substrates

Transmission electron microscopy has been employed to analyze the direct nucleation and growth, by plasma-assisted molecular beam epitaxy, of high quality InN (0001) In-face thin films on (111) Si substrates. Critical steps of the heteroepitaxial growth process are InN nucleation at low substrate temperature under excessively high N-flux conditions and subsequent growth of the main InN epilayer at the optimum conditions, namely, substrate temperature 400–450 °C and In/N flux ratio close to 1. InN nucleation occurs in the form of a very high density of three dimensional (3D) islands, which coalesce very fast into a low surface roughness InN film. The reduced reactivity of Si at low temperature and its fast coverage by InN limit the amount of unintentional Si nitridation by the excessively high nitrogen flux and good bonding/adhesion of the InN film directly on the Si substrate is achieved. The subsequent overgrowth of the main InN epilayer, in a layer-by-layer growth mode that enhances the lateral growth of InN, reduces significantly the crystal mosaicity and the density of threading dislocations is about an order of magnitude less compared to InN films grown using an AlN/GaN intermediate nucleation/buffer layer on Si. The InN films exhibit the In-face polarity and very smooth atomically stepped surfaces.

36 MATERIALS SCIENCE↗