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At least 379 records · Page 21

PDMS ‐silica composite gas separation membranes by direct ink writing

Abstract Polydimethylsiloxane (PDMS)‐based membranes containing amine‐functionalized and unfunctionalized silica particles were fabricated via direct ink writing for CO 2 /N 2 gas separation. The printability of the inks was evaluated by rheological measurements, while spectroscopy, microscopy, thermal measurements, and mechanical testing were employed to characterize the printed membranes. The surface morphology of the membranes revealed the absence of voids, demonstrating their suitability for gas separation. The printed membranes also exhibited desirable thermal and mechanical properties (i.e., thermal degradation temperature of 518 °C and tensile strength as high as 1.178 MPa with 529% elongation). The PDMS‐based membranes generally displayed high permeability for CO 2 but slightly low selectivity for the CO 2 /N 2 gas pair. The best‐combined permeability‐selectivity performance of 8794 barrer and selectivity of 11.64 was demonstrated by the printed PDMS membrane containing no SiO 2 fillers. The inclusion of unfunctionalized SiO 2 particles generally increased the membrane's gas permeability but compromised the selectivity. In contrast, membranes with amine‐functionalized silica showed improved selectivity compared to membranes containing unfunctionalized silica. Overall, the performance and characteristics offered by the PDMS/silica composite membranes demonstrated the potential of 3D printing as an economical and sustainable fabrication approach to developing materials for carbon capture applications.

Gutierrez, Dianne B.↗

An insight into microscopy and analytical techniques for morphological, structural, chemical, and thermal characterization of cellulose

Cellulose obtained from plants is a bio-polysaccharide and the most abundant organic polymer on earth that has immense household and industrial applications. Hence, the characterization of cellulose is important for determining its appropriate applications. In this article, we review the characterization of cellulose morphology, surface topography using microscopic techniques including optical microscopy, transmission electron microscopy, scanning electron microscopy, and atomic force microscopy. Additionally, other physicochemical characteristics like crystallinity, chemical composition, and thermal properties are studied using techniques including X-ray diffraction, Fourier transform infrared, Raman spectroscopy, nuclear magnetic resonance, differential scanning calorimetry, and thermogravimetric analysis. This review may contribute to the development of using cellulose as a low-cost raw material with anticipated physicochemical properties.

59 BASIC BIOLOGICAL SCIENCES↗

Persistent Structure and Frustrated Magnetism in High Entropy Rare-Earth Zirconates

The configurational complexity and distinct local atomic environments of high entropy oxides remain largely unexplored, leaving structure-property relationships and the hypothesis that the family offers rich tunability for applications ambiguous. This work investigates the influence of cation size and materials synthesis in determining the resulting structure and magnetic properties of a family of high entropy rare-earth zirconates (HEREZs, nominal composition RE 2 Zr 2 O 7 with RE = rare-earth element combinations including Eu, Gd, Tb, Dy, Ho, La, or Sc). Here, the structural characterization of the series is examined through synchrotron X-ray diffraction and pair distribution function analysis, and electron microscopy, demonstrating average defect-fluorite structures with considerable local disorder, in all samples. The surface morphology and particle sizes are found to vary significantly with preparation method, with irregular micron-sized particles formed by high temperature sintering routes, spherical nanoparticles resulting from chemical co-precipitation methods, and porous nanoparticle agglomerates resulting from polymer steric entrapment synthesis. In agreement with the disordered cation distribution found across all samples, magnetic measurements indicate that all synthesized HEREZs show frustrated magnetic behavior, as seen in a number of single-component RE 2 Zr 2 O 7 pyrochlore oxides. These findings advance the understanding of the local structure of high entropy oxides and demonstrate strategies for designing nanostructured morphologies in the class.

36 MATERIALS SCIENCE↗

Through‐Plane Conductive Hydrophobic Electrodes for CO 2 Electrolysis to Ethylene

Copper catalyst gas diffusion electrodes (GDEs) have demonstrated unique electrochemical selectivity converting CO 2 to C 2 -hydrocarbons such as ethylene and ethanol but have been challenged by their hydrophobic chemical stability and internal electrical resistance leading to low energy efficiency. Carbon-supported GDEs have low electrical resistance but lack sufficient stability at industrially relevant current densities. While polymer-supported GDEs have improved hydrophobicity, they also display high in-plane electrical resistance, particularly at industrial scales. Here, in this work, we demonstrate a composite gas diffusion layer that combines hydrophobic porous polymers with an electrically conductive backbone addressing these core gas diffusion electrode (GDE) scaling challenges. We investigate the material properties of standalone porous perfluoropolyether (PFPE) polymers, including porosity and surface morphology, under varying processing conditions and then incorporate these polymers into a porous copper foam. This composite enhances the mechanical rigidity necessary for cell assembly and provides a through-plane electrical conduction path to reduce electrical resistive losses. This enhanced PFPE composite GDE displays efficient CO 2 reduction, achieving 15% ethylene energy efficiency at 100 cm 2 . These findings contribute to the development of advanced catalyst materials and electrode architectures and promote scalable strategies for electrochemical conversion of CO 2 into high-value carbon products.

Chemistry↗

Enhancing Charge Transport of 2D Perovskite Passivation Agent for Wide-Bandgap Perovskite Solar Cells Beyond 21%

The replacement of a small amount of organic cations with bulkier organic spacer cations in the perovskite precursor solution to form a 2D perovskite passivation agent (2D-PPA) in 3D perovskite thin films has recently become a promising strategy for developing perovskite solar cells (PSCs) with long-term stability and high efficiency. However, the long, bulky organic cations often form a barrier, hindering charge transport. In this study, for the first time, 2D-PPA engineering based on wide-bandgap (~1.68?eV) perovskites are reported. Pentafluorophenethylammonium (F5PEA+) is introduced to partially replace phenylethylammonium (PEA+) as the 2D-PPA, forming a strong noncovalent interaction between the two bulky cations. The charge transport across and within the planes of pure 2D perovskites, based on mixed ammoniums, increases by a factor of five and three compared with that of mono-cation 2D perovskites, respectively. The perovskite films based on mixed-ammonium (F5PEA+-PEA+) 2D-PPA exhibit similar surface morphology and crystal structure, but longer carrier lifetime, lower exciton binding energy, less trap density and higher conductivity, in comparison with those using mono-cation (PEA+) 2D-PPA. The performance of PSCs based on mixed-cation 2D-PPA is enhanced from 19.58% to 21.10% along with improved stability, which is the highest performance for reported wide-bandgap PSCs.

14 SOLAR ENERGY↗

Extent of interlocking and metallurgical bonding in friction riveting of aluminum alloy to steel

In this study, the joining of 6061-T6 aluminum alloy and DP590 steel using a M42 steel rivet via friction riveting technique is investigated. The surface morphology and microstructure characterization reveal the formation of an anchor zone that imparts mechanical interlock as well as the formation of metallurgical bonds at the interface of aluminum and steel. A combination of interlocking and bonding results in the achievement of a high load-carrying capacity of 5.7 kN during lap shear testing at room temperature. A finite element-based computational model was developed which accurately predicted the lap shear response of the joint. The model revealed that the metallurgical bond formed during fric-riveting adds 39% peak load strength to the joint. An extensive microstructural investigation, post-lap-shear fractography, and the modeling results, together provided insights on the joint failure mechanism. In conclusion, this study highlights that friction riveting is a promising method for aluminum-to-steel dissimilar joining, which is important for lighweighing automotive vehicles for energy efficiency.

36 MATERIALS SCIENCE↗

Synthesis and Characterization of MoNb Films Superconducting at 100-200 mK

We have developed a new transition-edge sensor material with critical temperature (T-c) in the range 100-200 mK. The new material is a solid solution of two superconducting components, MoxNb1-x, co-sputtered from two high-purity single-component targets (Mo and Nb). The T-c has a minimum (dT(c)/dx = 0) at an intermediate concentration of the components. We have optimized the deposition parameters and composition to provide films with a sharp superconducting transition at ~ 150 mK. We investigated structural features of the films and surface morphology using X-ray diffraction (XRD) and scanning electron microscopy. The XRD measurements indicate that the grown films are polycrystalline, with a preferred orientation along the (110) crystal direction and a clear correlation between superconducting properties and film microstructure.

superconducting alloys↗

Melt Pool and Heat Treatment Optimization for the Fabrication of High-Strength and High-Toughness Additively Manufactured 4340 Steel

Additively manufactured (AM) components offer superior design flexibility compared to their conventionally manufactured counterparts, and optimizing processing parameters is key to achieving high-quality depositions with desirable and predictable mechanical properties. This study was focused on 4340 steel fabricated using laser powder bed fusion (LPBF), and 42 laser power and scan speed combinations have been systematically investigated to determine an optimized melt pool geometry that would ensure fully-dense parts. The AM material was compared with a wrought 4340 equivalent and studied in two customized heat treated conditions, optimized for strength and toughness, respectively. The microstructures of the as-fabricated and heat treated AM and wrought materials were characterized to assess differences introduced by the layer-by-layer fabrication process and subsequent heat treatment. Tensile properties of both materials were also evaluated and demonstrate that the AM materials offer equal or superior properties compared to the wrought equivalents. Differences in fracture surface morphologies indicate the distinct failure mechanisms associated with the materials’ characteristic microstructures, and the role of inclusions in the failures was studied to elucidate these differences. Complementary to the experimental investigations, the dataset was leveraged to make recommendations for future design of experiments to optimize AM build parameters in other material systems. A statistical Monte Carlo analysis was used to predict the interpolation error produced using reduced datasets and to enable informed processing parameters selection. These findings are discussed to make recommendations for the use of AM materials for high-integrity structural applications.

36 MATERIALS SCIENCE↗

Recent progresses on thermal–hydraulics evaluations of accident tolerant fuel cladding materials

Thermal–hydraulics (T-H) experiments have been on the progress to evaluate boiling heat transfer characteristics of accident tolerant fuel (ATF) candidates for further supporting the core-loading of these advanced ATF concepts in light water reactors (LWRs). Here this study covers recent experimental studies of ATF claddings and summarizes some significant results. Recent T-H experimental results of ATF cladding candidates demonstrated that the material thermal–physical properties have pronounced effects on critical heat flux (CHF). Such effects have not been well resolved in the current physics-governing models. These effects of cladding materials on CHF could be potentially rationalized by the material-conjugated boiling heat transfer, where the material-dominated heat conduction competes with the flow boiling-dominated heat convection. As progressively increasing the mass flux and/or liquid subcooling, CHF differences between different materials gradually decrease, which is in agreement with the recent T-H experimental results of ATF claddings. This is because the dominance of heat convection over heat conduction is primarily improved by liquid subcooling and/or mass flow rate. It is noteworthy that surface oxidization of claddings may have unknown impacts on T-H performances because the formation of oxide layers on cladding surfaces introduces variations of material thermal–physical properties and then changes the surface morphological features, which results in some difficulties in evaluating the thermal safety margins of ATF claddings.

36 MATERIALS SCIENCE↗

Structural properties of optically clear bacterial cellulose produced by Komagataeibacter hansenii using arabitol

Here, bacterial cellulose (BC) exhibits beneficial properties for use in biomedical applications but is limited by its lack of tunable transparency capabilities. To overcome this deficiency, a novel method to synthesize transparent BC materials using an alternative carbon source, namely arabitol, was developed. Characterization of the BC pellicles was performed for yield, transparency, surface morphology, and molecular assembly. Transparent BC was produced using mixtures of glucose and arabitol. Zero percent arabitol pellicles exhibited 25% light transmittance, which increased with increasing arabitol concentration through to 75% light transmittance. While transparency increased, overall BC yield was maintained indicating that the altered transparency may be induced on a micro-scale rather than a macro-scale. Significant differences in fiber diameter and the presence of aromatic signatures were observed. Overall, this research outlines methods for producing BC with tunable optical transparency, while also bringing new insight to insoluble components of exopolymers produced by Komagataeibacter hansenii.

59 BASIC BIOLOGICAL SCIENCES↗

Operando carbon corrosion measurements in fuel cells using boron-doped carbon supports

Carbonaceous materials are the most common catalyst supports in proton exchange membrane fuel cell (PEMFCs), yet their corrosion is one of the limiting factors in achieving high durability. Herein, we doped carbon supports with boron (B) to increase the corrosion-resistance of the support. Two types of B-doped carbons were synthesized and studied as platinum support materials. Further, they varied in their morphologies, surface areas, and the types of boron species. The durability of Pt/B-doped carbon catalysts was investigated using the US-DOE catalysts’ supports accelerated stress test (AST) and a mass-spectrometer connected to the fuel cell effluent stream to quantify the mass of corroded carbon support in operando. The addition of boron to the carbon increased the stability of Pt catalysts in long-term usage of PEMFC. After 4000 AST cycles, more than 50% of initial current density was preserved for the boron-containing systems, while less than 30% of it remained with Vulcan carbon (Pt/V). Also, the Pt/B-doped carbon samples demonstrated better electrochemical active surface area (ECSA) stability when compared to Pt/V. Carbon loss measurements showed that B-doped carbons have higher resistance to electrochemical corrosion than unmodified carbon. Specifically, the substitutional boron-doped carbon demonstrated an extremely high stability and low corrosion rate.

25 ENERGY STORAGE↗

Hemp fiber reinforced dual dynamic network vitrimer biocomposites with direct incorporation of amino silane

Natural fiber composites are inexpensive and renewable alternatives to traditional fiber reinforced polymers (FRPs). However, existing natural fiber composites primarily rely on petrochemical based thermosetting matrices, which are difficult to recycle due to their stable crosslinked network structures. To address this challenge, it is desirable to develop natural fiber composites with inherently recyclable biobased matrices. In this study, we developed a dual dynamic network vitrimer matrix from hempseed oil and limonene derivatives and demonstrated its application in hemp fiber reinforced composites. To improve the weak interface between hemp fiber and the polymer matrix, a common challenge in the realm of natural fiber composites, we directly incorporated amino silane into the vitrimer matrix. The amino silane participated in the polymer network, increasing the crosslink density and toughening the matrix, as evidenced by a significantly improved impact strength from 3.5 kJ/m 2 to 10.3 kJ/m 2 . Moreover, the incorporation of amino silane resulted in a lower water absorption by 11% in 7-day soaking for the composites, demonstrating improved fiber/matrix interfacial interaction. Furthermore, our biobased vitrimer matrix exhibits both imine and hydroxy-ester dynamic bonds, which enable the recycling of the biocomposite through a mild and cost-effective aminolysis process (100°C, 3h, ambient pressure). The decomposed polymer matrix was successfully reused as a polyol for polyurethane adhesives, and the surface morphology of recovered hemp fibers was analyzed and compared with that of the original fibers. Furthermore, these findings will help broaden the use of vitrimers for practical natural fiber composite applications, raise awareness of the problem of recycling natural fiber composite waste, and shed light on the interfacial challenge of natural fiber reinforced vitrimer composites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigation of B 4 C for inhibiting crystallization in silica at high temperatures

Amorphous silica has numerous high temperature applications due to its inherent thermal shock resistance and low coefficient of thermal expansion (CTE). However, at the high temperatures required for processing (>1200 °C), the metastable β-cristobalite phase preferentially forms and is accompanied by a volume change, and potential cracking, upon conversion to the low temperature α-cristobalite phase. The CTE of the final crystalline phase is an order of magnitude higher than its amorphous counterpart. Here experimental results demonstrate that small additions of B 4 C (3.5 wt%) effectively inhibit silica crystallization in powder and sintered gel-cast forms up to 22h at temperatures as high as 1500°C as confirmed via x-ray diffraction. Further, the oxidation of B 4 C to B 2 O 3 and its subsequent melt and evaporation disrupts the nucleation and growth of the cristobalite phase. The mechanism for crystallization inhibition is further explored through optical microscopy to probe changes in surface morphology.

36 MATERIALS SCIENCE↗

Sizing of discontinuous natural fibers: Effect of sizing approach and sizing concentration on composite properties

Natural fiber reinforced composites (NFRCs) are gaining attention in automotive applications as an alternative to glass fiber composites due to their lightweight and renewable sourcing. However, the inherent hydrophilicity of natural fibers leads to poor compatibility with hydrophobic polymers which adversely affects the mechanical properties of the composites and can limit their application to non-structural parts. Sizing is a common approach used for synthetic fibers to improve the interface between fiber and matrix. However, there is limited study on the sizing of natural fibers, and hence the focus of this work. Here, in this study, two different approaches to sizing discontinuous coir fibers were investigated, namely; (1) ex-situ sizing and (2) in-situ sizing. A commercial polypropylene (PP) based sizing agent was used and the effects of varying sizing solution concentrations (1.5, 2.5, and 3.5 wt%) on the properties of the composites was studied. Results showed that composites prepared via the in-situ sizing process had better fiber–matrix adhesion and improved tensile properties compared to ex-situ sized composites. On studying the effect of different sizing concentrations on composite properties, we found that the tensile strength of the composites increased (by ∼ 42 %) up to 2.5 wt% sizing concentration (in solution) and then decreased. However, the impact strength decreased significantly on increasing the sizing content beyond 1.5 wt% (by ∼ 40 %). Additionally, the study was further extended to investigate the effect of sizing on different NFRCs (coir, banana, and cottonized hemp fiber) where effectiveness of sizing was found to be influenced by the fiber surface morphology.

36 MATERIALS SCIENCE↗

High-speed synchrotron X-ray phase-contrast imaging for evaluating microscale damage mechanisms and tracking cracking behaviors inside cross-ply GFRCs

In this study, we integrated the high-speed synchrotron X-ray phase-contrast imaging (PCI) with a modified Kolsky compression bar loading platform to visualize the dynamic failure processes of cross-ply glass fiber reinforced composites (GFRCs). Four S-2 glass/SC-15 composite specimens were prepared, having similar thicknesses but different stacking sequences, namely as [0 12 /90 12 ], [90 12 /0 12 ], [0 8 /90 8 /0 8 ], and [90 8 /0 8 /90 8 ]. Three-dimensional synchrotron X-ray computed tomography and scanning electron microscopy (SEM) were employed to examine the microstructures and quantify the fiber volume fractions. Each specimen was notched and subjected to a dynamic three-point flexural loading. The onset of cracking close to the notch tip, crack propagation in 0° or 90° plies and their interface, crack opening, and ultimately failure of the specimen were captured by high-speed synchrotron X-ray PCI. Additional dynamic experiments were performed to determine the average time when the stress wave propagated through the specimen and correlate the X-ray images with the specimen's force-deflection response. Finally, the surface morphology of each specimen after the dynamic loading was imaged by SEM. Comparison between real-time X-ray images and post-fracture SEM images demonstrated the capability of the X-ray method to record damage evolution inside composites. Furthermore, the high spatial and temporal resolutions of the X-ray setup and edge enhancement by PCI enabled the identification of microscale damage features within 1 μs. Two damaging processes were identified, crack growth was quantified, and fracture toughness of the composites was evaluated. The method is deemed useful to reveal microscale damage mechanisms and track cracking behaviors inside cross-ply GFRCs under dynamic loading in real time.

42 ENGINEERING↗

Degradation mechanism of lead-vanado-iodoapatite in NaCl solution

Degradation mechanism of lead-vanado-iodoapatite (IAPT) in NaCl solution at 90 °C was investigated through systematic characterization of surface morphology, microstructure and microchemistry evolution of the alteration layer. Nano-scale characterization indicated that IAPT crystals degraded from grain boundaries toward inner grains, forming ultrafine Cl-bearing crystallites. A coupled interface dissolution-reprecipitation replacement mechanism and the ion exchange between Cl - and I - across the degradation zone may together play roles in determining the nano-scale degradation behavior of IAPT. This work highlights the degradation through multiple reactions and elemental transport across the liquid-solid and solid-solid interfaces at length scales from sub-millimeter to nanoscale.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗