arXiv subjects

Ilja Gunkel

Publications and source records attributed to Ilja Gunkel.

6 recordsLinked to original sources

arXiv2023

Anoplophora graafi Longhorn Beetle Coloration is due to Disordered Diamond-like Packed Spheres

While artificially photonic materials are typically highly ordered, photonic structures in many species of birds and insects do not possess a long-range order. Studying their order-disorder interplay sheds light on the origin of the photonic band gap. Here, we investigated the scale morphology of the Anoplophora graafi longhorn beetle. Combining small-angle X-ray scattering and slice-and-view FIB-SEM tomography with molecular dynamics and optical simulations, we characterised the chitin sphere assemblies within blue and green. A. graafi scales. The low volume fraction of spheres and the number of their nearest neighbours are incompatible with any known close-packed sphere morphology. A short-range diamond lattice with long-range disorder best describes the sphere assembly, which will inspire the development of new colloid-based photonic materials.

physics.optics↗

arXiv2023

X-ray nanotomography reveals formation of single diamonds by block copolymer self-assembly

Block copolymers are recognised as a valuable platform for creating nanostructured materials with unique properties. Morphologies formed by block copolymer self-assembly can be transferred into a wide range of inorganic materials, enabling applications including energy storage and metamaterials. However, imaging of the underlying, often complex, nanostructures in large volumes has remained a challenge, limiting progress in materials development. Taking advantage of recent advances in X-ray nanotomography, we non-invasively imaged exceptionally large volumes of nanostructured soft materials at high resolution, revealing a single diamond morphology in a triblock terpolymer composite network. This morphology, which is ubiquitous in nature, has so far remained elusive in block copolymers, despite its potential to create materials with large photonic bandgaps. The discovery was made possible by the precise analysis of distortions in a large volume of the self-assembled diamond network, which are difficult to unambiguously assess using traditional characterisation tools. We anticipate that high-resolution X-ray nanotomography, which allows imaging of much larger sample volumes than electron-based tomography, will become a powerful tool for the quantitative analysis of complex nanostructures and that structures such as the triblock terpolymer-directed single diamond will enable the generation of advanced multicomponent composites with hitherto unknown property profiles.

cond-mat.soft↗

arXiv2023

High-resolution three-dimensional imaging of topological textures in single-diamond networks

Highly periodic structures are often said to convey the beauty of nature. However, most material properties are strongly influenced by the defects they contain. On the mesoscopic scale, molecular self-assembly exemplifies this interplay; thermodynamic principles determine short-range order, but long-range order is mainly impeded by the kinetic history of the material and by thermal fluctuations. For the development of self-assembly technologies, it is imperative to characterise and understand the interplay between self-assembled order and defect-induced disorder. Here we used synchrotron-based hard X-ray nanotomography to reveal a pair of extended topological defects within a self-assembled single-diamond network morphology. These defects are morphologically similar to the comet and trefoil patterns of equal and opposite half-integer topological charges observed in liquid crystals and appear to maintain a constant separation across the thickness of the sample, resembling pairs of full vortices in superconductors and other hard condensed matter systems. These results are expected to open new windows to study defect formation in soft condensed matter, particularly in biological systems where most structures are formed by self-assembly.

cond-mat.soft↗

arXiv2020

Strong Circular Dichroism in Single Gyroid Optical Metamaterials

Over the past two decades, metamaterials have led to an increasing number of biosensing and nanophotonic applications due to the possibility of a careful control of light propagating through subwavelength features. Chiral nanostructures (characterized by the absence of any mirror symmetry), in particular, give rise to unique chiro-optical properties such as circular dichroism and optical activity. Here, we present a gyroid optical metamaterial with a periodicity of 65 nm exhibiting a strong circular dichroism at visible wavelengths. Our bottom-up approach, based on metallic replication of the gyroid morphology in triblock terpolymer films, generates a large area of periodic optical metamaterials. We observe a strong circular dichroism in gold and silver gyroid metamaterials at visible wavelengths. We show that the circular dichroism is inherently linked to the handedness of the gyroid nanostructure, and demonstrate its tuneability. The optical effects are discussed and compared to other existing systems, showing the potential of bottom-up approaches for large-scale circular filters and chiral sensing.

physics.optics↗

arXiv2019

Surface Reconstruction Limited Conductivity in Block-Copolymer Li Battery Electrolytes

Solid polymer electrolytes for lithium batteries promise improvements in safety and energy density if their conductivity can be increased. Nanostructured block copolymer electrolytes specifically have the potential to provide both good ionic conductivity and good mechanical properties. This study shows that the previously neglected nanoscale composition of the polymer electrolyte close to the electrode surface has an important effect on impedance measurements, despite its negligible extent compared to the bulk electrolyte. Using standard stainless steel blocking electrodes, the impedance of lithium salt-doped poly(isoprene-b-styrene-b-ethylene oxide) (ISO) exhibited a marked decrease upon thermal processing of the electrolyte. In contrast, covering the electrode surface with a low molecular weight poly(ethylene oxide) (PEO) brush resulted in higher and more reproducible conductivity values, which were insensitive to the thermal history of the device. A qualitative model of this effect is based on the hypothesis that ISO surface reconstruction at the different electrode surfaces leads to a change in the electrostatic double layer, affecting electrochemical impedance spectroscopy measurements. As a main result, PEO-brush modification of electrode surfaces is beneficial for the robust electrolyte performance of PEO-containing block-copolymers and may be crucial for their accurate characterization and use in Li-ion batteries.

physics.app-ph↗

arXiv2017

Semicrystalline block copolymers in rigid confining nanopores

We have investigated PLLA crystallization in lamellae-forming PS-b-PLLA confined to straight cylindrical nanopores under weak confinement (nanopore diameter D / equilibrium PS-b-PLLA period L0 larger than 4.8). Molten PS-b-PLLA predominantly forms concentric lamellae along the nanopores, but intertwined helices occur even for D/L0 = 7.3. Quenching PS-b-PLLA melts below TG(PS) results in PLLA cold crystallization strictly confined by the vitrified PS domains. Above TG(PS), PLLA crystallization is templated by the PS-b-PLLA melt domain structure in the nanopore centers, while adsorption on the nanopore walls stabilizes the outermost cylindrical PS-b-PLLA shell. In between, the nanoscopic PS-b-PLLA melt domain structure apparently ripens to reduce frustrations transmitted from the outermost immobilized PS-b-PLLA layer. The onset of PLLA crystallization catalyzes the ripening while transient ripening states are arrested by advancing PLLA crystallization. Certain helical structure motifs persist PLLA crystallization even if PS is soft. The direction of fastest PLLA crystal growth is preferentially aligned with the nanopore axes to the same degree as for PLLA homopolymer, independent of whether PS is vitreous or soft.

cond-mat.soft↗