Search Results
Crystalline Carbosilane-Based Block Copolymers: Synthesis by Anionic Polymerization and Morphology Evaluation in the Bulk State
Block copolymers (BCPs) in the bulk state are known to self-assemble into different morphologies depending on their polymer segment ratio. For polymers with amorphous and crystalline BCP segments, the crystallization process can be influenced significantly by the corresponding bulk morphology. Herein, the synthesis of the amorphous-crystalline BCP poly(dimethyl silacyclobutane)-block-poly(2vinyl pyridine), (PDMSB-b-P2VP), by living anionic polymerization is reported. Polymers with overall molar masses ranging from 17 400 g to 592 200 g mol−1 and PDMSB contents of 4.8–83.9 vol% are synthesized and characterized by size-exclusion chromatography and NMR spectroscopy. The bulk morphology of the obtained polymers is investigated by means of transmission electron microscopy and small angle X-ray scattering, revealing a plethora of self-assembled structures, providing confined and nonconfined conditions. Subsequently, the influence of the previously determined morphologies and their resulting confinement on the crystallinity and crystallization behavior of PDMSB is analyzed via differential scanning calorimetry and powder X-ray diffraction. Here, fractionated crystallization and supercooling effects are observable as well as different diffraction patterns of the PDMSB crystallites for confined and nonconfined domains.
Flexible and transparent electrodes imprinted from metal nanostructures: morphology and opto-electronic performance
We directed the self-assembly of nanoscale colloids via direct nanoimprint lithography to create flexible transparent electrodes (FTEs) with metal line widths below 3 μm in a roll-to-roll-compatible process. Gold nanowires and nanospheres with oleylamine shells were imprinted with soft silicone stamps, arranged into grids of parallel lines, and converted into metal lines in a plasma process. We studied the hierarchical structure and opto-electronic performance of the resulting grids as a function of particle geometry and concentration. The performance in terms of optical transmittance was dominated by the line width. Analysis of cross-sections indicated that plasma sintering only partially removed the insulating ligands and formed lines with thin conductive shells and a non-conductive core. We provide evidence that the self-assembly of high-aspect nanowires can compensate for defects of the stamp and substrate irregularities during imprinting, while spheres cannot. The wire-based electrodes thus outperformed the sphere-based electrodes at ratios of optical transmittance to sheet resistance of up to ≈ 0.9% Ωsq−1, while spheres only reached ≈ 0.55% Ωsq−1
Toward a Li-Ion Battery Ontology Covering Production and Material Structure
An ontology for the structured storage, retrieval, and analysis of data on lithium-ion battery materials and electrode-to-cell production is presented. It provides a logical structure that is mapped onto a digital architecture and used to visualize, correlate, and make predictions in battery production, research, and development. Materials and processes are specified using a predetermined terminology; a chain of unit processes (steps) connects raw materials and products (items) of battery cell production. The ontology enables the attachment of analytical methods (characterization methods) to items. Workshops and interviews with experts in battery materials and production processes are conducted to ensure that the structure is conformable both for industrial-scale and laboratory-scale data generation and implementation. Raw materials and intermediate products are identified and defined for all steps to the final battery cell. Steps and items are defined based on current standard materials and process chains using terms that are in common use. Alternative structures and the connection of the ontology to other existing ontologies are discussed. The contribution provides a pragmatic, accessible way to unify the storage of materials-oriented lithium-ion battery production data. It aids the linkage of such data with domain knowledge and the automation of data analysis in production and research.
Microscopic Softening Mechanisms of an Ionic Liquid Additive in an Electrically Conductive Carbon-Silicone Composite
The microstructural changes caused by the addition of the ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide to polydimethylsiloxane (PDMS) elastomer composites filled with carbon black (CB) are analyzed to explain the electrical, mechanical, rheological, and optical properties of IL-containing precursors and composites. Swelling experiments and optical analysis indicate a limited solubility of the IL in the PDMS matrix that reduces the cross-linking density of PDMS both globally and locally, which reduces the Young's moduli of the composites. A rheological analysis of the precursor mixture shows that the IL reduces the strength of carbon–carbon and carbon–PDMS interactions, thus lowering the filler–matrix coupling and increasing the elongation at break. Electromechanical testing reveals a combination of reversible and irreversible piezoresistive responses that is consistent with the presence of IL at microscopic carbon–carbon interfaces, where it enables re-established electrical connections after stress release but reduces the absolute conductivity.
Dynamic Light Scattering on Nanoparticles in Microgravity in a Drop Tower
Gravity affects colloidal dispersions via sedimentation and convection. We used dynamic light scattering (DLS) to quantify the mobility of nanoparticles on ground and in microgravity. A DLS instrument was adapted to withstand the accelerations in a drop tower, and a liquid handling set-up was connected in order to stabilize the liquid temperature and enable rapid cooling or heating. Light scattering experiments were performed in the drop tower at ZARM (Bremen, Germany) during a microgravity interval of 9.1 s and compared to measurements on ground. Particle dynamics were analyzed at constant temperature and after a rapid temperature drop using a series of DLS measurements with 1 s integration time. We observed nanoparticles with average gold core diameters of 7.8 nm and non-polar oleylamine shells that were dispersed in tetradecane and had an average hydrodynamic diameter of 21 nm. The particles did not change their diameter in the observed temperature range. The particle dynamics inferred from DLS on ground and in microgravity were in good agreement, demonstrating the possibility to perform reliable DLS measurements in a drop tower.
Flexible and transparent electrodes imprinted from Au nanowires: stability and ageing
We study the stability of flexible transparent electrodes (FTEs) that were self-assembled from ultra-thin gold nanowires (AuNW) by direct nanoimprinting of inks with different particle concentrations (1 to 10 mg mL−1). The resulting lines were less than 3 μm wide and contained bundles of AuNW with oleylamine (OAm) ligand shells. Small-angle X-ray scattering confirmed a concentration-independent bundle structure. Plasma sintering converted the wire assemblies into lines with a thin metal shell that contributes most to electrical conductivity and covers a hybrid core. We studied the relative change in sheet resistance and the morphology of the FTEs with time. The sheet resistance increased at all concentrations, but at different rates. The metal shell aged by de-wetting and pore formation. The hybrid core de-mixed and densified, which led to a partial collapse of the shell. Residual organics migrated through the shell via its pores. Lines formed at low concentration (cAu = 2 to 3 mg mL−1) contained less residual organics and aged slower than those formed at high cAu ≥ 5 mg mL−1. We passivated the conductive shell with thin, adsorbed layers of PEDOT:PSS and found that it decelerated degradation by slowing surface diffusion and hindering further rupture of the shell. Thick capping layers prevented degradation entirely and stopped pore formation.
Soft electronics by inkjet printing metal inks on porous substrates
Soft electronic devices enable new types of products for an ergonomic interaction of humans with a digital environment. The inkjet (droplet on demand) printing of electrically conductive ink in plural on soft substrates such as paper, textile, and polymers is a promising route for the prototyping and small-scale production of soft electronics that is efficient, cost-saving, and provides a rapid turnaround due to its fully digital workflow. The choice of materials and processing parameters is challenging, however, due to the combined complexity of metal-containing inks, their dynamics during droplet ejection, the active role of the porous substrate, and possible post-deposition steps. This review focuses on recent developments in inkjet printing of metal inks onto soft, porous substrates and their applications. The first section discusses the general principles in the inkjet printing of metal inks, including drop formation and jetting, wetting, and post treatment processes. The second section deals with the effect that the porosity of substrates has on the drying, diffusion, and adhesion of inks. Finally, current challenges and achievements of inkjet-printed, metal-containing inks are discussed.
Precipitate number density determination in microalloyed steels by complementary atom probe tomography and matrix dissolution
Particle number densities are a crucial parameter in the microstructure engineering of microalloyed steels. We introduce a new method to determine nanoscale precipitate number densities of macroscopic samples that is based on the matrix dissolution technique (MDT) and combine it with atom probe tomography (APT). APT counts precipitates in microscopic samples of niobium and niobium-titanium microalloyed steels. The new method uses MDT combined with analytical ultracentrifugation (AUC) of extracted precipitates, inductively coupled plasma–optical emission spectrometry, and APT. We compare the precipitate number density ranges from APT of 137.81 to 193.56 × 1021 m−3 for the niobium steel and 104.90 to 129.62 × 1021 m−3 for the niobium-titanium steel to the values from MDT of 2.08 × 1021 m−3 and 2.48 × 1021 m−3. We find that systematic errors due to undesired particle loss during extraction and statistical uncertainties due to the small APT volumes explain the differences. The size ranges of precipitates that can be detected via APT and AUC are investigated by comparison of the obtained precipitate size distributions with transmission electron microscopy analyses of carbon extraction replicas. The methods provide overlapping resulting ranges. MDT probes very large numbers of small particles but is limited by errors due to particle etching, while APT can detect particles with diameters below 10 nm but is limited by small-number statistics. The combination of APT and MDT provides comprehensive data which allows for an improved understanding of the interrelation between thermo-mechanical controlled processing parameters, precipitate number densities, and resulting mechanical-technological material properties. Graphical abstract: [Figure not available: see fulltext.]
A block copolymer templated approach for the preparation of nanoporous polymer structures and cellulose fiber hybrids by ozone treatment
Functional amphiphilic block copolymers (BCPs) are versatile, smart, and promising materials that are often used as soft templates in nanoscience. BCPs generally feature the capability of microphase-separation leading to various interesting morphologies at the nanometer length scale. Materials derived from BCPs can be converted into porous structures while retaining the underlying morphology of the matrix material. Here, a convenient and scalable approach for the fabrication of porous functional polyvinylpyridines (P2VP) is introduced. The BCP polyisoprene-block-P2VP (PI-b-P2VP) is obtained via sequential anionic polymerization of the respective monomers and used to form either BCP films in the bulk state or a soft template in a composite with cellulose fibers. Cross-linking of the BCPs with 1,4-diiodobutane is conducted and subsequently PI domains are selectively degraded inside the materials using ozone, while preserving the porous and tailor-made P2VP nanostructure. Insights into the feasibility of the herein presented strategy is supported by various polymer characterization methods comprising nuclear magnetic resonance (NMR), size exclusion chromatography (SEC), and differential scanning calorimetry (DSC). The resulting bulk- and composite materials are investigated regarding their morphology and pore formation by scanning electron microscopy (SEM), atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS). Furthermore, chemical conversions were examined by energy dispersive X-ray spectroscopy (EDS), attenuated total reflection Fourier-transformation infrared spectroscopy (ATR-FTIR) and water contact angle (WCA) measurements. By this convenient strategy the fabrication of functional porous P2VP in the bulk state and also within sustainable cellulose composite materials is shown, paving the synthetic strategy for the generation of a new family of stimuli-responsive sustainable materials.
Advancing environmental intelligence through novel approaches in soft bioinspired robotics and allied technologies: I-Seed project position paper for Environmental Intelligence in Europe
The EU-funded FET Proactive Environmental Intelligence project "I-Seed"(Grant Agreement n. 101017940, https://www.iseedproject.eu/) targets towards the development of a radically simplified and environmentally friendly approach for environmental monitoring. Specifically, I-Seed aims at developing a new generation of self-deployable and biodegradable soft miniaturized robots, inspired by the morphology and dispersion abilities of plant seeds, able to perform low-cost, environmentally responsible, in-situ measurements. The natural functional mechanisms of seeds dispersal offer a rich source of robust, highly adaptive, mass and energy efficient mechanisms, and behavioral and morphological intelligence, which can be selected and implemented for advanced, but simple, technological inventions. I-Seed robots are conceived as unique in their movement abilities because inspired by passive mechanisms and materials of natural seeds, and unique in their environmentally friendly design because made of all biodegradable components. Sensing is based on a chemical transduction mechanism in a stimulus-responsive sensor material with fluorescence-based optical readout, which can be read via one or more drones equipped with fluorescent LiDAR technology and a software able to perform a real time georeferencing of data. The I-Seed robotic ecosystem is envisioned to be used for collecting environmental data in-situ with high spatial and temporal resolution across large remote areas where no monitoring data are available, and thus for extending current environmental sensor frameworks and data analysis systems.