Multilayer Amorphous‐Si‐B‐C‐N/γ‐Al2O3/α‐Al2O3 Membranes for Hydrogen Purification

The hydrogen and carbon monoxide separation is an important step in the hydrogen production process. If H₂ can be selectively removed from the product side during hydrogen production in membrane reactors, then it would be possible to achieve complete CO conversion in a single‐step under high temperature conditions. In the present work, the multilayer amorphous‐Si‐B‐C‐N/γ‐Al₂O₃/α‐Al₂O₃ membranes with gradient porosity have been realized and assessed with respect to the thermal stability, geometry of pore space and H₂/CO permeance. The α‐Al₂O₃ support has a bimodal pore‐size distribution of about 0.64 and 0.045 µm being macroporous and the intermediate γ‐Al₂O₃ layer—deposited from boehmite colloidal dispersion—has an average pore‐size of 8 nm being mesoporous. The results obtained by the N₂‐adsorption method indicate a decrease in the volume of micropores—0.35 vs. 0.75 cm³ g^?1—and a smaller pore size ?6.8 vs. 7.4 Å—in membranes with the intermediate mesoporous γ‐Al₂O₃ layer if compared to those without. The three times Si‐B‐C‐N coated multilayer membranes show higher H₂/CO permselectivities of about 10.5 and the H₂ permeance of about 1.05 × 10^?8 mol m^?2 s^?1 Pa^?1. If compared to the state of the art of microporous membranes, the multilayer Si‐B‐C‐N/γ‐Al₂O₃/α‐Al₂O₃ membranes are appeared to be interesting candidates for hydrogen separation because of their tunable nature and high‐temperature and high‐pressure stability.     

Short fatigue cracks in intermetallic γ‐TiAl‐alloys

Fatigue crack growth at room temperature and its relation to the local microstructure is studied for four different γ‐TiAl‐alloys with microstructures ranging from coarse and fully lamellar to fine and partly lamellar. It is shown that the number of cycles to failure depends strongly on the efficiency of the first barrier to crack extension, as crack growth rates may increase rapidly once this barrier has been breached by a specific crack. The crack extension behaviour for two typical barriers (colony boundary and twin boundary) is studied using high‐resolution optical and scanning electron microscopy.     

3‐D Integrated All‐Solid‐State Rechargeable Batteries

Portable society urgently calls for integrated energy supplies. This holds for autonomous devices but even more so for future medical implants. Evidently, rechargeable integrated all‐solid‐state batteries will play a key role in these fields, enabling miniaturization, preventing electrode degradation upon cycling and electrolyte leakage. Planar solid‐state thin film batteries are rapidly emerging but reveal several potential drawbacks, such as a relatively low energy density and the use of highly reactive lithium. Thin film Si‐intercalation electrodes covered with a solid‐state electrolyte are found to combine a high storage capacity of 3500 mAh g^–1 with high cycle life, enabling to integrate batteries in Si. Based on the excellent intercalation chemistry of Si, a new 3D‐integrated all‐solid‐state battery concept is proposed. High aspect ratio cavities and features, etched in silicon, will yield large surface area batteries with anticipated energy density of about 5 mWh μm^–1 cm^–2, i.e. more than 3 orders of magnitude higher than that of integrated capacitors.     

Investigation of In Situ and Conventional Post‐Weld Heat Treatments on Dual‐Laser‐Beam‐Welded γ‐TiAl‐Based Alloy

This paper describes a way to improve the microstructure and mechanical properties of welding seams by in situ and conventional post‐weld heat treatments for laser beam welding of the Ti–45Al–5Nb–0.2C–0.2B alloy. The seams are crack‐free with reduced longitudinal residual stress and higher elongation to fraction after post‐weld heat treatment. The welding zone consists of α₂ after welding, transforms to a massive γ during in situ post‐weld heat treatment, and finally forms a convoluted microstructure after conventional heating. The phase composition across the welding zone is discussed.     

A Cut‐and‐Paste Approach to 3D Graphene‐Oxide‐Based Architectures

Properly cut sheets can be converted into complex 3D structures by three basic operations including folding, bending, and pasting to render new functions. Folding and bending are extensively employed in crumpling, origami, and pop‐up fabrications for 3D structures. Pasting joins different parts of a material together, and can create new geometries that are fundamentally unattainable by folding and bending. However, it has been much less explored, likely due to limited choice of weldable thin film materials and residue‐free glues. Here it is shown that graphene oxide (GO) paper is one such suitable material. Stacked GO sheets can be readily loosened up and even redispersed in water, which upon drying, restack to form solid structures. Therefore, water can be utilized to heal local damage, glue separated pieces, and release internal stress in bent GO papers to fix their shapes. Complex and dynamic 3D GO architectures can thus be fabricated by a cut‐and‐paste approach, which is also applicable to GO‐based hybrid with carbon nanotubes or clay sheets.     

Processing and Applications of Intermetallic γ‐TiAl‐Based Alloys

Development and processing of high‐temperature materials is the key to technological advancements in engineering areas where materials have to meet extreme requirements. Examples for such areas are the aerospace and spacecraft industry or the automotive industry. New structural materials have to be “stronger, stiffer, hotter, and lighter” to withstand the extremely demanding conditions in the next generation of aircraft engines, space vehicles, and automotive engines. Intermetallic γ‐TiAl‐based alloys show a great potential to fulfill these demands.     

Reaction‐Diffusion‐Mediated Photolithography for Designing Pseudo‐3D Microstructures

Microstructures with 3D features provide advanced functionalities in many applications. Reaction‐diffusion process has been employed in photolithography to produce pseudo‐3D microstructures in a reproducible manner. In this work, the influences of various parameters on growth behavior of polymeric structures are investigated and the use of the reaction‐diffusion‐mediated photolithography (RDP) is expanded to a wide range of structural dimensions. In addition, how a lens effect alters the growth behavior of microstructures in conjunction with reaction‐diffusion process is studied. For small separation between reaction sites in the array, ultraviolet (UV) exposure time is optimized along with the separation to avoid film or plateau formation. It is further proved that the RDP process is highly reproducible and applicable to various photocurable resins. In a demonstrative purpose, the use of microdomes created by the RDP process as microlens arrays is shown. The RDP process enables the production of pseudo‐3D microstructures even with collimated UV light in the absence of complex optical setups, thereby potentially serving as a useful means to create micropatterns and particles with unique structural features.     

Facile Synthesis of γ‐In2Se3 Nanoflowers toward High Performance Self‐Powered Broadband γ‐In2Se3/Si Heterojunction Photodiode

An effective colloidal process involving the hot‐injection method is developed to synthesize uniform nanoflowers consisting of 2D γ‐In₂Se₃ nanosheets. By exploiting the narrow direct bandgap and high absorption coefficient in the visible light range of In₂Se₃, a high‐quality γ‐In₂Se₃/Si heterojunction photodiode is fabricated. This photodiode shows a high photoresponse under light illumination, short response/recovery times, and long‐term durability. In addition, the γ‐In₂Se₃/Si heterojunction photodiode is self‐powered and displays a broadband spectral response ranging from UV to IR with a high responsivity and detectivity. These excellent performances make the γ‐In₂Se₃/Si heterojunction very interesting as highly efficient photodetectors.     

Biotinylated Photopolymers for 3D‐Printed Unibody Lab‐on‐a‐Chip Optical Platforms

The present work reports the first demonstration of straightforward fabrication of monolithic unibody lab‐on‐a‐chip (ULOCs) integrating bioactive micrometric 3D scaffolds by means of multimaterial stereolithography (SL). To this end, a novel biotin‐conjugated photopolymer is successfully synthesized and optimally formulated to achieve high‐performance SL‐printing resolution, as demonstrated by the SL‐fabrication of biotinylated structures smaller than 100 µm. By optimizing a multimaterial single‐run SL‐based 3D‐printing process, such biotinylated microstructures are incorporated within perfusion microchambers whose excellent optical transparency enables real‐time optical microscopy analyses. Standard biotin‐binding assays confirm the existence of biotin‐heads on the surfaces of the embedded 3D microstructures and allow to demonstrate that the biofunctionality of biotin is not altered during the SL‐printing, thus making it exploitable for further conjugation with other biomolecules. As a step forward, an in‐line optical detection system is designed, prototyped via SL‐printing and serially connected to the perfusion microchambers through customized world‐to‐chip connectors. Such detection system is successfully employed to optically analyze the solution flowing out of the microchambers, thus enabling indirect quantification of the concentration of target interacting biomolecules. The successful application of this novel biofunctional photopolymer as SL‐material enables to greatly extend the versatility of SL to directly fabricate ULOCs with intrinsic biofunctionality.     

3D‐Printing Electrolytes for Solid‐State Batteries

Solid‐state batteries have many enticing advantages in terms of safety and stability, but the solid electrolytes upon which these batteries are based typically lead to high cell resistance. Both components of the resistance (interfacial, due to poor contact with electrolytes, and bulk, due to a thick electrolyte) are a result of the rudimentary manufacturing capabilities that exist for solid‐state electrolytes. In general, solid electrolytes are studied as flat pellets with planar interfaces, which minimizes interfacial contact area. Here, multiple ink formulations are developed that enable 3D printing of unique solid electrolyte microstructures with varying properties. These inks are used to 3D‐print a variety of patterns, which are then sintered to reveal thin, nonplanar, intricate architectures composed only of Li₇La₃Zr₂O₁₂ solid electrolyte. Using these 3D‐printing ink formulations to further study and optimize electrolyte structure could lead to solid‐state batteries with dramatically lower full cell resistance and higher energy and power density. In addition, the reported ink compositions could be used as a model recipe for other solid electrolyte or ceramic inks, perhaps enabling 3D printing in related fields.     

Sustainable Solid‐State Supercapacitors Made of 3D‐Poly(3,4‐ethylenedioxythiophene) and κ‐Carrageenan Biohydrogel

3D‐Poly(3,4‐ethylenedioxythiophene) (PEDOT) electrodes are prepared using the multi‐step template‐assisted approach. Specifically, poly(lactic acid) nano‐ and microfibers collected on a previously polymerized PEDOT film are used as templates for PEDOT nano‐ and microtubes, respectively. Morphological analysis of the samples indicates that 3D‐PEDOT electrodes obtained using a low density of templates, in which nano‐ and microtubes are clearly identified, exhibit higher porosity, and specific surface than conventional 2D‐PEDOT electrodes. However, a pronounced leveling effect is observed when the density of templates is high. Thus, electrodes with microtubes still present a 3D‐morphology but much less marked than those prepared using a low density of PLA microfibers, whereas the morphology of those with nanotubes is practically identical to that of films. Electrochemical studies prove that solid supercapacitors prepared using 3D‐PEDOT electrodes and κ‐carrageenan biohydrogel as electrolytic medium, exhibit higher ability to exchange charge reversibly and to storage charge than the analogues prepared with 2D‐electrodes. Furthermore, solid devices prepared using 3D‐electrodes and κ‐carrageenan biohydrogel exhibit very similar specific capacitances that those obtained using the same electrodes and a liquid electrolyte (i.e., acetonitrile solution with 0.1 M LiClO₄). These results prove that the success of 3D‐PEDOT electrodes is independent of the electrolytic medium.

     

Local deformation at micro‐notches and crack initiation in an intermetallic γ‐TiAl‐alloy

The relation is studied between crack initiation from micro‐notches in a fully lamellar intermetallic γ‐TiAl alloy and the local strain field. These micro‐notches were introduced using femtosecond‐laser ablation and had dimensions below the average colony size. The specimen under investigation was then subjected to fatigue loading. Continuous monitoring using a travelling optical microscope allowed detecting microcracks at an early stage. Prior to fatigue loading, a sustained load was applied and the local strain field was determined using digital image correlation. This was supplemented by a Finite Element analysis of the notches and their neighbourhood. It was found that a crack was initiated from a notch causing high normal strains in lamella direction, whereas no crack was initiated from notches with high shear strains.