Multifunctional Aluminum Pre-treatments from End-Functionalized Phosphonic Acid Self-Assembled Monolayers.

Aluminum alloys are used in advanced engineering applications as they possess a combination of favorable properties, including high strength, lightweightness, good corrosion resistance, machineability, and recyclability. Such applications often require forming the sheets into the final components, which is typically aided by an oil-based lubricant, followed by joining them using adhesives, which is hampered by residual lubricant. In this work, aluminum surfaces were modified with different self-assembled monolayers (SAMs), with the goal of significantly reducing the amount of lubricant while simultaneously improving friction properties, forming, and bonding performance. Our results show that SAMs terminated with hydrophilic and nucleophilic end groups give rise to high-energy surfaces with wetting properties that are stable over time. These surfaces showed significantly improved surface wetting by the lubricant, which in turn resulted in an improved forming performance at reduced lubricant coat weights. Moreover, the nucleophilic SAM termination provided outstanding performance in adhesive bonding tests under corrosive conditions.

Synthesis of polysiloxane elastomers modified with sulfonyl side groups and their electromechanical response.

Dielectric elastomer transducers are elastic capacitors that respond to mechanical or electrical stress. They can be used in applications such as millimeter-sized soft robots and harvesters of the energy contained in ocean waves. The dielectric component of these capacitors is a thin elastic film, preferably made of a material having a high dielectric permittivity. When properly designed, these materials convert electrical energy into mechanical energy and vice versa, as well as thermal energy into electrical energy and vice versa. Whether a polymer can be used for one or the other application is determined by its glass transition temperature (Tg), which should be significantly below room temperature for the former and around room temperature for the latter function. Herein, we report a polysiloxane elastomer modified with polar sulfonyl side groups to contribute to this field with a powerful new material. This material has a dielectric permittivity as high as 18.4 at 10 kHz and 20 °C, a relatively low conductivity of 5 × 10-10 S cm-1, and a large actuation strain of 12% at an electric field of 11.4 V µm-1 (0.25 Hz and 400 V). At 0.5 Hz and 400 V, the actuator showed a stable actuation of 9% over 1000 cycles. The material exhibited a Tg of -13.6 °C, which although is well below room temperature affected the material's response in actuators, which shows significant differences in the response at different frequencies and temperatures and in films with different thicknesses.

Thermoplastic Toughening of a Semiaromatic Polyamide with an Amino-telechelic Polyethylene.

Semiaromatic polyamides are used for metal replacement in advanced engineering applications to reduce weight and improve efficiency, but their range of application is limited by their inherent lack of ductility and toughness. Here, we combined semiaromatic polyamide poly(hexamethylene terephthalamide-co-isophthalamide) (PA6TI) with up to 30 wt % amine-terminated polyethylene (PE(NH2)2) by high-temperature melt compounding, which was suggested to lead to the formation of PA-PE block copolymers at the interface between the PE(NH2)2 and the PA6TI. This resulted in PA6TI/PE(NH2)2 blends with smaller, more uniform particle sizes than in PA6TI blended with nonfunctional PE or the commercial impact modifier, maleic anhydride-functionalized styrene-ethylene-butylene-styrene (SEBS) under the same conditions. The PA6TI/PE(NH2)2 blends and the corresponding glass fiber-reinforced composites consequently showed significantly greater increases in room-temperature tensile ductility and fracture energy with respect to unmodified PA6TI, as well as maintained mechanical stability at high temperatures, and only modest decreases in stiffness and strength, even at high PE(NH2)2 contents. These improvements were attributed to the crystallinity of the PE(NH2)2 particles and to improved morphological stabilization and matrix-particle adhesion, consistent with the presence of PA-PE block copolymer at the matrix-particle interfaces.

Reversible Microscale Assembly of Nanoparticles Driven by the Phase Transition of a Thermotropic Liquid Crystal.

The arrangement of nanoscale building blocks into patterns with microscale periodicity is challenging to achieve via self-assembly processes. Here, we report on the phase-transition-driven collective assembly of gold nanoparticles in a thermotropic liquid crystal. A temperature-induced transition from the isotropic to the nematic phase under anchoring-driven planar alignment leads to the assembly of individual nanometer-sized particles into arrays of micrometer-sized agglomerates, whose size and characteristic spacing can be tuned by varying the cooling rate. Phase field simulations coupling the conserved and nonconserved order parameters exhibit a similar evolution of the morphology as the experimental observations. This fully reversible process offers control over structural order on the microscopic level and is an interesting model system for the programmable and reconfigurable patterning of nanocomposites with access to micrometer-sized periodicities.

Spontaneous formation of a self-healing carbon nanoskin at the liquid-liquid interface.

Biological membranes exhibit the ability to self-repair and dynamically change their shape while remaining impermeable. Yet, these defining features are difficult to reconcile with mechanical robustness. Here, we report on the spontaneous formation of a carbon nanoskin at the oil-water interface that uniquely combines self-healing attributes with high stiffness. Upon the diffusion-controlled self-assembly of a reactive molecular surfactant at the interface, a solid elastic membrane forms within seconds and evolves into a continuous carbon monolayer with a thickness of a few nanometers. This nanoskin has a stiffness typical for a 2D carbon material with an elastic modulus in bending of more than 40-100 GPa; while brittle, it shows the ability to self-heal upon rupture, can be reversibly reshaped, and sustains complex shapes. We anticipate such an unusual 2D carbon nanomaterial to inspire novel approaches towards the formation of synthetic cells with rigid shells, additive manufacturing of composites, and compartmentalization in industrial catalysis.

Transient Elastomers with High Dielectric Permittivity for Actuators, Sensors, and Beyond.

Dielectric elastomers (DEs) are key materials in actuators, sensors, energy harvesters, and stretchable electronics. These devices find applications in important emerging fields such as personalized medicine, renewable energy, and soft robotics. However, even after years of research, it is still a great challenge to achieve DEs with increased dielectric permittivity and fast recovery of initial shape when subjected to mechanical and electrical stress. Additionally, high dielectric permittivity elastomers that show reliable performance but disintegrate under normal environmental conditions are not known. Here, we show that polysiloxanes modified with amide groups give elastomers with a dielectric permittivity of 21, which is 7 times higher than regular silicone rubber, a strain at break that can reach 150%, and a mechanical loss factor tan δ below 0.05 at low frequencies. Actuators constructed from these elastomers respond to a low electric field of 6.2 V µm-1, giving reliable lateral actuation of 4% for more than 30 000 cycles at 5 Hz. One survived 450 000 cycles at 10 Hz and 3.6 V µm-1. The best actuator shows 10% lateral strain at 7.5 V µm-1. Capacitive sensors offer a more than a 6-fold increase in sensitivity compared to standard silicone elastomers. The disintegrated material can be re-cross-linked when heated to elevated temperatures. In the future, our material could be used as dielectric in transient actuators, sensors, security devices, and disposable electronic patches for health monitoring.

Blatter-type radicals as polarizing agents for electrochemical overhauser dynamic nuclear polarization.

Overhauser dynamic nuclear polarization (O-DNP) refers to a microwave-assisted process where an unpaired electron's (e.g. a radical) spin polarization is transferred to surrounding nuclei in solution, thus increasing the nuclear magnetic resonance (NMR) signal intensity of a given substance by several orders of magnitude. The presence of the unpaired electrons, which induces relaxation of the resulting hyperpolarized state when the radiation is halted, can be avoided by electrochemically removing the radicals on demand. We report the use of Blatter-type (benzo[e][1,2,4]triazinyl) radicals as polarizing agents, potentially opening the way to highly tunable radicals for electrochemical DNP.

Lamellar carbon-aluminosilicate nanocomposites with macroscopic orientation.

Novel preparative approaches towards lamellar nanocomposites of carbon and inorganic materials are relevant for a broad range of technological applications. Here, we describe how to utilize the co-assembly of a liquid-crystalline hexaphenylene amphiphile and an aluminosilicate precursor to prepare carbon-aluminosilicate nanocomposites with controlled lamellar orientation and macroscopic order. To this end, the shear-induced alignment of a precursor phase of the two components resulted in thin films comprising lamellae with periodicities on the order of the molecular length scale, an "edge-on" orientation relative to the substrate and parallel to the shearing direction with order on the centimeter length scale. The lamellar structure, orientation, and macroscopic alignment were preserved in the subsequent pyrolysis that yielded the corresponding carbon-aluminosilicate nanocomposites.

Structure-Property Relationships in Bithiophenes with Hydrogen-Bonded Substituents.

The use of crystal engineering to control the supramolecular arrangement of π-conjugated molecules in the solid-state is of considerable interest for the development of novel organic electronic materials. In this study, we investigated the effect of combining of two types of supramolecular interaction with different geometric requirements, amide hydrogen bonding and π-interactions, on the π-overlap between calamitic π-conjugated cores. To this end, we prepared two series of bithiophene diesters and diamides with methylene, ethylene, or propylene spacers between the bithiophene core and the functional groups in their terminal substituents. The hydrogen-bonded bithiophene diamides showed significantly denser packing of the bithiophene cores than the diesters and other known α,ω-disubstituted bithiophenes. The bithiophene packing density reach a maximum in the bithiophene diamide with an ethylene spacer, which had the smallest longitudinal bithiophene displacement and infinite 1D arrays of electronically conjugated, parallel, and almost linear N-H⋅⋅⋅O=C hydrogen bonds. The synergistic hydrogen bonding and π-interactions were attributed to the favorable conformation mechanics of the ethylene spacer and resulted in H-type spectroscopic aggregates in solid-state absorption spectroscopy. These results demonstrate that the optoelectronic properties of π-conjugated materials in the solid-state may be tailored systematically by side-chain engineering, and hence that this approach has significant potential for the design of organic and polymer semiconductors.

Optical gap and fundamental gap of oligoynes and carbyne.

The optoelectronic properties of various carbon allotropes and nanomaterials have been well established, while the purely sp-hybridized carbyne remains synthetically inaccessible. Its properties have therefore frequently been extrapolated from those of defined oligomers. Most analyses have, however, focused on the main optical transitions in UV-Vis spectroscopy, neglecting the frequently observed weaker optical bands at significantly lower energies. Here, we report a systematic photophysical analysis as well as computations on two homologous series of oligoynes that allow us to elucidate the nature of these weaker transitions and the intrinsic photophysical properties of oligoynes. Based on these results, we reassess the estimates for both the optical and fundamental gap of carbyne to below 1.6 eV, significantly lower than previously suggested by experimental studies of oligoynes.

Crystallization and Organic Field-Effect Transistor Performance of a Hydrogen-Bonded Quaterthiophene.

Crystalline thin films of π-conjugated molecules are relevant as the active layers in organic electronic devices. Therefore, materials with enhanced control over the supramolecular arrangement, crystallinity, and thin-film morphology are desirable. Herein, it is reported that hydrogen-bonded substituents serve as additional structure-directing elements that positively affect crystallization, thin-film morphology, and device performance of p-type organic semiconductors. It is observed that a quaterthiophene diacetamide exhibits a denser packing than that of other quaterthiophenes in the single-crystal structure and, as a result, displays enhanced intermolecular electronic interactions. This feature was preserved in crystalline thin films that exhibited a layer-by-layer morphology, with large domain sizes and high internal order. As a result, organic field-effect transistors of these polycrystalline thin films showed mobilities in the range of the best mobility values reported for single-crystalline quaterthiophenes. The use of hydrogen-bonded groups may, thus, provide an avenue for organic semiconducting materials with improved morphology and performance.

Long-Lived Photocharges in Supramolecular Polymers of Low-Band-Gap Chromophores.

Photoinduced charge separation in supramolecular aggregates of π-conjugated molecules is a fundamental photophysical process and a key criterion for the development of advanced organic electronics materials. Herein, the self-assembly of low-band-gap chromophores into helical one-dimensional aggregates, due to intermolecular hydrogen bonding, is reported. Chromophores confined in these supramolecular polymers show strong excitonic coupling interactions and give rise to charge-separated states with unusually long lifetimes of several hours and charge densities of up to 5 mol % after illumination with white light. Two-contact devices exhibit increased photoconductivity and can even show Ohmic behavior. These findings demonstrate that the confinement of organic semiconductors into one-dimensional aggregates results in a considerable stabilization of charge carriers for a variety of π-conjugated systems, which may have implications for the design of future organic electronic materials.

Hexayne Amphiphiles and Bolaamphiphiles.

Oligoynes with two or more conjugated carbon-carbon triple bonds are useful precursors for carbon-rich nanomaterials. However, their range of applications has so far been severely limited by the challenging syntheses, particularly in the case of oligoynes with functional groups. Here, we report a universal synthetic approach towards both symmetric and unsymmetric, functionalized hexaynes through the use of a modified Eglinton-Galbraith coupling and a sacrificial building block. We demonstrate the versatility of this approach by preparing hexaynes functionalized with phosphonic acid, carboxylic acid, ammonium, or thiol head groups, which serve as neutral, cationogenic, or anionogenic interfacially active groups. We show that these hexaynes are carbon-rich amphiphiles or bolaamphiphiles that self-assemble at liquid-liquid interfaces, on solid surfaces, as well as in aqueous media.

Unusually Long-Lived Photocharges in Helical Organic Semiconductor Nanostructures.

Photocharge generation and formation of long-lived charge carriers are relevant in photosynthesis, photocatalysis, photovoltaics, and organic electronics. A better understanding of the factors that determine these processes in synthetic polymer semiconductors is crucial, but difficult due to their morphological inhomogeneity. Here, we report the formation of exceptionally long-lived photocharges in one-dimensional organic semiconductor nanostructures. These nanostructures consist of chiral oligopeptide-substituted thienothiophene-based chromophores and exhibit a well-defined helical arrangement of these chromophores at their core. The chromophores give rise to spectroscopic H-aggregates and show strong intermolecular excitonic coupling. We demonstrate that all of these parameters are the prerequisites required for the nanostructures to show the efficient formation of polaron-like photocharges upon irradiation with a low-power white light source. The observed charge carriers in the helical nanowires show an unusually long lifetime on the order of several hours and are formed at high concentrations of up to 3 mol % in the absence of any dedicated electron acceptor. They are observed in solution as well as in film and furthermore give rise to a light-induced increase of the macroscopic charge transport. By contrast, no such photocharge generation is observed either in non-aggregating reference systems of the same chromophores or in aggregated but non-helical systems that do not form one-dimensional nanostructures. Our results thus demonstrate a clear correlation between nanoscopic confinement and the generation of long-lived photocharges.

Erratum: Uniform electroactive fibre-like micelle nanowires for organic electronics.

This corrects the article DOI: 10.1038/ncomms15909.

Uniform electroactive fibre-like micelle nanowires for organic electronics.

Micelles formed by the self-assembly of block copolymers in selective solvents have attracted widespread attention and have uses in a wide variety of fields, whereas applications based on their electronic properties are virtually unexplored. Herein we describe studies of solution-processable, low-dispersity, electroactive fibre-like micelles of controlled length from π-conjugated diblock copolymers containing a crystalline regioregular poly(3-hexylthiophene) core and a solubilizing, amorphous regiosymmetric poly(3-hexylthiophene) or polystyrene corona. Tunnelling atomic force microscopy measurements demonstrate that the individual fibres exhibit appreciable conductivity. The fibres were subsequently incorporated as the active layer in field-effect transistors. The resulting charge carrier mobility strongly depends on both the degree of polymerization of the core-forming block and the fibre length, and is independent of corona composition. The use of uniform, colloidally stable electroactive fibre-like micelles based on common π-conjugated block copolymers highlights their significant potential to provide fundamental insight into charge carrier processes in devices, and to enable future electronic applications.

Self-Assembled Monolayers as Patterning Tool for Organic Electronic Devices.

The patterning of functional materials represents a crucial step for the implementation of organic semiconducting materials into functional devices. Classical patterning techniques such as photolithography or shadow masking exhibit certain limitations in terms of choice of materials, processing techniques and feasibility for large area fabrication. The use of self-assembled monolayers (SAMs) as a patterning tool offers a wide variety of opportunities, from the region-selective deposition of active components to guiding the crystallization direction. Here, we discuss general techniques and mechanisms for SAM-based patterning and show that all necessary components for organic electronic devices, i.e., conducting materials, dielectrics, organic semiconductors, and further functional layers can be patterned with the use of self-assembled monolayers. The advantages and limitations, and potential further applications of patterning approaches based on self-assembled monolayers are critically discussed.

Templating for hierarchical structure control in carbon materials.

Carbon-based materials show a remarkable variety of physical properties. For this reason, they have recently been explored for many advanced applications and emerging technologies. In the absence of actual "chemical" functionalities in these materials, tailoring these physical properties requires control on all levels of the structural hierarchy, from the atomic structure (carbon connectivity, defects, impurities), to the supramolecular level (domain orientations), nanoscopic length scale (domain sizes, porosity), microscopic structure (morphology), and macroscopic aspects (shape, surface chemistry). When preparing carbon materials, all these features can be tailored through the use of hard, soft, or molecular templates. Based on such templating approaches or through their combination, tremendous progress towards hierarchically structured carbon materials has recently been accomplished. Novel carbon nanomaterials such as brick-walled carbon tubes, carbon nanotube forests, coral-like carbon monoliths, or functional carbon nanosheets have become available, some of which exhibit unusual combinations of electronic, mechanical, and chemical properties. This review aims to discuss how the different templating approaches allow the control of structure formation on various length scales, how hierarchical structure formation can be realized, and which challenges remain, such as the detailed control over the carbon connectivity or the surface chemistry.

Preparation of Carbon Nanosheets at Room Temperature.

Amphiphilic molecules equipped with a reactive, carbon-rich "oligoyne" segment consisting of conjugated carbon-carbon triple bonds self-assemble into defined aggregates in aqueous media and at the air-water interface. In the aggregated state, the oligoynes can then be carbonized under mild conditions while preserving the morphology and the embedded chemical functionalization. This novel approach provides direct access to functionalized carbon nanomaterials. In this article, we present a synthetic approach that allows us to prepare hexayne carboxylate amphiphiles as carbon-rich siblings of typical fatty acid esters through a series of repeated bromination and Negishi-type cross-coupling reactions. The obtained compounds are designed to self-assemble into monolayers at the air-water interface, and we show how this can be achieved in a Langmuir trough. Thus, compression of the molecules at the air-water interface triggers the film formation and leads to a densely packed layer of the molecules. The complete carbonization of the films at the air-water interface is then accomplished by cross-linking of the hexayne layer at room temperature, using UV irradiation as a mild external stimulus. The changes in the layer during this process can be monitored with the help of infrared reflection-absorption spectroscopy and Brewster angle microscopy. Moreover, a transfer of the carbonized films onto solid substrates by the Langmuir-Blodgett technique has enabled us to prove that they were carbon nanosheets with lateral dimensions on the order of centimeters.