Polymer Based Nanocomposites: Effect of Filler‐Filler and Filler‐Matrix Interactions

Nanocomposite materials present specific features, mainly due to their very high interfacial area, and a very short distance between reinforcing particles surface. For polymer based nanocomposites, reinforcing particles are most of the time much stiffer than the matrix. In that case, the percolation of those particles which occurs at a threshold fraction which depends on their shape factor (and on their dispersion characteristics) is shown to play a drastic role, especially if they form a rigid network. Such a network may result from strong interactions between the surface of the dispersed particles, but softer network may appear if the particles are bound together through the interactions of their surface with polymer chains. In order to analyze and to predict the behavior of nanocomposite materials, a modeling of this type of interactions is proposed, and allows to better understand the origin of the high reinforcing effect, generally observed. However, the complete prediction of composite materials with percolating dispersed fillers is still a difficult problem and requires further developments. It exemplifies for the special case of composites a general problem of two phase materials: the effect of scaling down the reinforcement and the properties of entangled structures.     

Enhanced Grain Refinement Through Deformation Induced α Precipitation in Hot Working of α + β Titanium Alloy

This study reports a novel forging process to fabricate bulk fine‐grained (grain size ≈ 1 µm) Ti–6Al–4V alloy, in which temperatures near the β transus (T_β) and strain rates around 0.15 s^?1 are used for the deformation. The formation of fine‐grained microstructure is mainly result from the deformation‐induced precipitation of α grains from the β matrix.     

Dipolar‐Distribution Cavity γ‐Fe2O3@C@α‐MnO2 Nanospindle with Broadened Microwave Absorption Bandwidth by Chemically Etching

Developing microwave absorption materials with ultrawide bandwidth and low density still remains a challenge, which restricts their actual application in electromagnetic signal anticontamination and defense stealth technology. Here a series of olive‐like γ‐Fe₂O₃@C core–shell spindles with different shell thickness and γ‐Fe₂O₃@C@α‐MnO₂ spindles with different volumes of dipolar‐distribution cavities were successfully prepared. Both series of absorbers exhibit excellent absorption properties. The γ‐Fe₂O₃@C@α‐MnO₂ spindle with controllable cavity volume exhibits an effective absorption (2O₃@C spindle reaches as high as ?45 dB because of the optimized electromagnetic impedance balance between polymer shell and γ‐Fe₂O₃ core. Intrinsic ferromagnetism of the anisotropy spindle is confirmed by electron holography. Strong coupling of magnetic flux stray lines between spindles is directly imaged. This unique morphology and facile etching technique might facilitate the study of core–shell type microwave absorbers.     

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.     

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.