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.     

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.     

In Situ Study of γ‐TiAl Lamellae Formation in Supersaturated α2‐Ti3Al Grains

In situ heating transmission electron microscopy (TEM) was used to investigate the initial stage of γ‐TiAl lamellae formation in an intermetallic Ti–45Al–7.5Nb alloy (in at.%). The material was heat treated and quenched in a non‐equilibrium state to consist mainly of supersaturated, ordered α₂‐Ti₃Al grains. Subsequently, specimens were annealed inside a TEM up to 750 °C. The in situ TEM study revealed that ultra‐fine γ‐TiAl laths precipitate in the α₂‐matrix at ≈730 °C which exhibit the classical Blackburn orientation relationship, i.e. (0001)α₂//(111)γ and [$11{\bar {2}}0$ ]α₂//<110]γ. The microstructural development observed in the in situ TEM experiment is compared to results from conventional ex situ TEM studies. In order to investigate the precipitation behavior of the γ‐phase with a complementary method, in situ high energy X‐ray diffraction experiments were performed which confirmed the finding that γ‐laths start to precipitate at ≈730 °C from the supersaturated α₂‐matrix.     

Amyloid Self‐Assembly of hIAPP8‐20 via the Accumulation of Helical Oligomers, α‐Helix to β‐Sheet Transition,and Formation of β‐Barrel Intermediates

The self‐assembly of human islet amyloid polypeptide (hIAPP) into β‐sheet‐rich nanofibrils is associated with the pathogeny of type 2 diabetes. Soluble hIAPP is intrinsically disordered with N‐terminal residues 8–17 as α‐helices. To understand the contribution of the N‐terminal helix to the aggregation of full‐length hIAPP, here the oligomerization dynamics of the hIAPP fragment 8–20 (hIAPP8‐20) are investigated with combined computational and experimental approaches. hIAPP8‐20 forms cross‐β nanofibrils in silico from isolated helical monomers via the helical oligomers and α‐helices to β‐sheets transition, as confirmed by transmission electron microscopy, atomic force microscopy, circular dichroism spectroscopy, Fourier transform infrared spectroscopy, and reversed‐phase high performance liquid chromatography. The computational results also suggest that the critical nucleus of aggregation corresponds to hexamers, consistent with a recent mass‐spectroscopy study of hIAPP8‐20 aggregation. hIAPP8‐20 oligomers smaller than hexamers are helical and unstable, while the α‐to‐β transition starts from the hexamers. Converted β‐sheet‐rich oligomers first form β‐barrel structures as intermediates before aggregating into cross‐β nanofibrils. This study uncovers a complete picture of hIAPP8‐20 peptide oligomerization, aggregation nucleation via conformational conversion, formation of β‐barrel intermediates, and assembly of cross‐β protofibrils, thereby shedding light on the aggregation of full‐length hIAPP, a hallmark of pancreatic beta‐cell degeneration.     

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.     

Coaggregation of κ‐Casein and β‐Lactoglobulin Produces Morphologically Distinct Amyloid Fibrils

The unfolding, misfolding, and aggregation of proteins lead to a variety of structural species. One form is the amyloid fibril, a highly aligned, stable, nanofibrillar structure composed of β‐sheets running perpendicular to the fibril axis. β‐Lactoglobulin (β‐Lg) and κ‐casein (κ‐CN) are two milk proteins that not only individually form amyloid fibrillar aggregates, but can also coaggregate under environmental stress conditions such as elevated temperature. The aggregation between β‐Lg and κ‐CN is proposed to proceed via disulfide bond formation leading to amorphous aggregates, although the exact mechanism is not known. Herein, using a range of biophysical techniques, it is shown that β‐Lg and κ‐CN coaggregate to form morphologically distinct co‐amyloid fibrillar structures, a phenomenon previously limited to protein isoforms from different species or different peptide sequences from an individual protein. A new mechanism of aggregation is proposed whereby β‐Lg and κ‐CN not only form disulfide‐linked aggregates, but also amyloid fibrillar coaggregates. The coaggregation of two structurally unrelated proteins into cofibrils suggests that the mechanism can be a generic feature of protein aggregation as long as the prerequisites for sequence similarity are met.     

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.

     

Patterning π‐Conjugated Polymers

π‐Conjugated polymers show promise as active materials in application areas such as microelectronics, electro‐optics, opto‐electronics, and photonics. A critical feature in this emerging technology is device fabrication and the reproducible deposition of active material. This review focuses on current trends in the spatial deposition of conjugated polymers.     

Oxidation protective coatings for γ‐TiAl – recent trends

Engine designers show continued interest in γ‐TiAl based titanium aluminides as light–weight structural materials to be used at moderately elevated temperatures. Although alloy development has made significant progress in terms of mechanical properties and environmental resistance, protective coatings have been developed that help to extend the lifetime of these alloys significantly. The major challenge of coating development is to prevent the formation of fast growing titania. Furthermore, changes of coating chemistries at high temperatures have to be considered in order to avoid rapid degradation of the coatings due to interdiffusion between substrate and coating. The paper describes recent work of the authors on different coatings produced by means of magnetron sputter technique. Thin ceramic Ti‐Al‐Cr‐Y‐N layers tested at 900 °C exhibited poor oxidation resistance. In contrast, intermetallic Ti‐Al‐Cr, Si‐based and aluminum rich Ti‐Al coatings were tested at exposure temperatures up to 950 °C for 1000h resulting in reasonable and partially excellent oxidation behaviour.