Multiscale Experimental Mechanics of Hierarchical Carbon‐Based Materials

Investigation of the mechanics of natural materials, such as spider silk, abalone shells, and bone, has provided great insight into the design of materials that can simultaneously achieve high specific strength and toughness. Research has shown that their emergent mechanical properties are owed in part to their specific self‐organization in hierarchical molecular structures, from nanoscale to macroscale, as well as their mixing and bonding. To apply these findings to manmade materials, researchers have devoted significant efforts in developing a fundamental understanding of multiscale mechanics of materials and its application to the design of novel materials with superior mechanical performance. These efforts included the utilization of some of the most promising carbon‐based nanomaterials, such as carbon nanotubes, carbon nanofibers, and graphene, together with a variety of matrix materials. At the core of these efforts lies the need to characterize material mechanical behavior across multiple length scales starting from nanoscale characterization of constituents and their interactions to emerging micro‐ and macroscale properties. In this report, progress made in experimental tools and methods currently used for material characterization across multiple length scales is reviewed, as well as a discussion of how they have impacted our current understanding of the mechanics of hierarchical carbon‐based materials. In addition, insight is provided into strategies for bridging experiments across length scales, which are essential in establishing a multiscale characterization approach. While the focus of this progress report is in experimental methods, their concerted use with theoretical‐computational approaches towards the establishment of a robust material by design methodology is also discussed, which can pave the way for the development of novel materials possessing unprecedented mechanical properties.     

A Free‐Standing and Self‐Healable 2D Supramolecular Material Based on Hydrogen Bonding: A Nanowire Array with Sub‐2‐nm Resolution

In many 2D materials reported thus far, the forces confining atoms in a 2D plane are often strong interactions, such as covalent bonding. Herein, the first demonstration that hydrogen (H)‐bonding can be utilized to assemble polydiacetylene (a conductive polymer) toward a 2D material, which is stable enough to be free‐standing, is shown. The 2D material is well characterized by a large number of techniques (mainly different microscopy techniques). The H‐bonding allows splitting of the material into ribbons, which can reassemble, similar to a zipper, leading to the first example of a healable 2D material. Moreover, such technology can easily create 2D, organic, conductive nanowire arrays with sub‐2‐nm resolution. This material may have potential applications in stretchable electronics and nanowire cross‐bar arrays.     

Single‐Particle Tracking for Understanding Polydisperse Nanoparticle Dispersions

Colloidal dispersions of nanomaterials are often polydisperse in size, significantly complicating their characterization. This is particularly true for materials early in their historical development due to synthetic control, dispersion efficiency, and instability during storage. Because a wide range of system properties and technological applications depend on particle dimensions, it remains an important problem in nanotechnology to identify a method for the routine characterization of polydispersity in nanoparticle samples, especially changes over time. Commonly employed methods such as dynamic light scattering or analytical ultracentrifugation (AUC) accurately estimate only the first moment of the distribution or are not routine. In this work, the use of single‐particle tracking (SPT) to probe size distributions of common nanoparticle dispersions, including polystyrene nanoparticles, single‐walled carbon nanotubes, graphene oxide, chitosan‐tripolyphosphate, acrylate, hexagonal boron nitride, and poly(lactic‐co‐glycolic acid), is proposed and explored. The analysis of particle tracks is conducted using a newly developed Bayesian algorithm that is called Maximum A posteriori Nanoparticle Tracking Analysis. By combining SPT and AUC techniques, it is shown that it is possible to independently estimate the mean aspect ratio of anisotropic particles, an important characterization property. It is concluded that SPT provides a facile, rapid analytical method for routine nanomaterials characterization.     

Herstellung und komplexe Charakterisierung von Metall‐Keramik‐Verbundschichten

Formation and characterization of metal‐ceramic coatings The influence of the formation process and used materials of metal‐ceramic coatings on the structural properties of the deposited layers were investigated and optimized to increase the mechanical properties. There the deposition of the metal‐ceramic‐layers occurred by a combination of electrophoretic and galvanic deposition with siloxane as bonding compound. Layers with a high ceramic content were successfully created. As ceramic components commercial silicon carbide and silicon nitride were used. Nickel and Copper respectively were applied as metal component to fill the porous ceramic structure with the aim to increase the strength of the layers, where nevertheless a pre nickel‐plating or pre cupper plating of the steel substrate X6Cr17 before ceramic component deposition had to be done to increase the adhesion of the layers. The layer characterization was made by optical microscopy and scanning and transmission electron microscopy, where especially the bonding of the single particles by the siloxane was in evidence.     

Ideal Three‐Dimensional Electrode Structures for Electrochemical Energy Storage

Three‐dimensional electrodes offer great advantages, such as enhanced ion and electron transport, increased material loading per unit substrate area, and improved mechanical stability upon repeated charge–discharge. The origin of these advantages is discussed and the criteria for ideal 3D electrode structure are outlined. One of the common features of ideal 3D electrodes is the use of a 3D carbon‐ or metal‐based porous framework as the structural backbone and current collector. The synthesis methods of these 3D frameworks and their composites with redox‐active materials are summarized, including transition metal oxides and conducting polymers. The structural characteristics and electrochemical performances are also reviewed. Synthesis of composite 3D electrodes is divided into two types — template‐assisted and template‐free methods — depending on whether a pre‐made template is required. The advantages and drawbacks of both strategies are discussed.     

Metallo‐Supramolecular Block Copolymers

Supramolecular copolymers have become of increasing interest in recent years for the search of new materials with tunable properties. In particular, metallo‐supramolecular block copolymers—copolymers in which the blocks are linked together by a metal–ligand complex—have seen important progresses, allowing better control over the synthetic strategies for various architectures, and providing a better understanding of the parameters governing their self‐assembly. We review here recent developments on the synthesis and self‐assembly of such materials achieved in this field.     

Direct Imaging of the Induced‐Fit Effect in Molecular Self‐Assembly

Molecular recognition is a crucial driving force for molecular self‐assembly. In many cases molecules arrange in the lowest energy configuration following a lock‐and‐key principle. When molecular flexibility comes into play, the induced‐fit effect may govern the self‐assembly. Here, the self‐assembly of dicyanovinyl‐hexathiophene (DCV6T) molecules, a prototype specie for highly efficient organic solar cells, on Au(111) by using low‐temperature scanning tunneling microscopy and atomic force microscopy is investigated. DCV6T molecules assemble on the surface forming either islands or chains. In the islands the molecules are straight—the lowest energy configuration in gas phase—and expose the dicyano moieties to form hydrogen bonds with neighbor molecules. In contrast, the structure of DCV6T molecules in the chain assemblies deviates significantly from their gas‐phase analogues. The seemingly energetically unfavorable bent geometry is enforced by hydrogen‐bonding intermolecular interactions. Density functional theory calculations of molecular dimers quantitatively demonstrate that the deformation of individual molecules optimizes the intermolecular bonding structure. The intermolecular bonding energy thus drives the chain structure formation, which is an expression of the induced‐fit effect.     

Solving inverse electromagnetic problems using FDTD and gradient‐based minimization

We address time‐domain inverse electromagnetic scattering for determining unknown characteristics of an object from observations of the scattered field. Applications include non‐destructive characterization of media and optimization of material properties, for example, the design of radar absorbing materials. Another application is model reduction where a detailed model of a complex geometry is reduced to a simplified model. The inverse problem is formulated as an optimal control problem where the cost function to be minimized is the difference between the estimated and observed fields, and the control parameters are the unknown object characteristics. The problem is solved in a deterministic gradient‐based optimization algorithm using a parallel 2D FDTD scheme. Highly accurate analytical gradients are computed from the adjoint formulation. The inverse method is applied to the characterization of layered dispersive media and the determination of parameters in subcell models for thin sheets and narrow slots. Copyright © 2006 John Wiley & Sons, Ltd.     

Tough and Water‐Insensitive Self‐Healing Elastomer for Robust Electronic Skin

An electronic (e‐) skin is expected to experience significant wear and tear over time. Therefore, self‐healing stretchable materials that are simultaneously soft and with high fracture energy, that is high tolerance of damage or small cracks without propagating, are essential requirements for the realization of robust e‐skin. However, previously reported elastomers and especially self‐healing polymers are mostly viscoelastic and lack high mechanical toughness. Here, a new class of polymeric material crosslinked through rationally designed multistrength hydrogen bonding interactions is reported. The resultant supramolecular network in polymer film realizes exceptional mechanical properties such as notch‐insensitive high stretchability (1200%), high toughness of 12 000 J m^?2, and autonomous self‐healing even in artificial sweat. The tough self‐healing materials enable the wafer‐scale fabrication of robust and stretchable self‐healing e‐skin devices, which will provide new directions for future soft robotics and skin prosthetics.     

On the Anisotropy of Lotus‐Type Porous Copper

This paper addresses the thermal and mechanical properties of lotus‐type porous copper. Due to their cellular metal characteristics in combination with strong anisotropy, lotus‐type materials exhibit unique properties. As an example, directional thermal conduction enables the controlled transport of thermal energy in the pore direction without the need of strong thermal insulation. In this paper, thermal and mechanical finite element analyses are performed. The effective thermal conductivity, Young's modulus, and the 0.2%‐offset yield strength are determined. Special consideration is given to the anisotropy of the material. In order to guarantee accurate discretization of the complex material geometry, calculation models are directly based on computed microtomography data. Elastic properties are compared to experimental data and good agreement is found. For the characterization of the thermal anisotropy, a second numerical approach, called the Lattice Monte Carlo method, is used along with thermal finite element analysis. In addition to the numerical methods, the analytical Maxwell, Dulynev, and Bruggeman models are applied. Good agreement for the application of two‐dimensional versions of Dulynev's and Bruggeman models is observed whereas the Maxwell model significantly overestimates the material properties.     

Easy‐to‐clean Schichten – spezielle Anwendungen

Easy to clean surfaces – special applications Easy to clean surfaces can be made by wet‐chemical coating with subsequent heat‐treatment. Organically modified metal oxide films form the base reinforced by nano composite structures. The hydro‐ and oleophobic effect is obtained by perfluorinated organic molecule chains in the nano composite sol‐gel coatings. Application specific materials can be synthesized by the proper choice of suitable starting compounds and process parameters. The resulting coatings consist of a three‐dimensional cross‐linked inorganic part (such as a silica network) combined with an organic part. The organic material acts either as a surface modifier (example: alkyl, phenyl) or as crosslinker (example: acrylic, epoxy). The properties of such coating systems can be adjusted to obtain a wide range of glass‐ceramic or polymer‐like properties. The incorporation of nanoparticles into these materials significantly enhances the abrasion and the scratch resistance. Such coatings mainly on metal parts are used in diagnostics, analytical chemistry and medical technology.     

Adaptable and Reprogrammable Surfaces

Establishing control over chemical reactions on interfaces is a key challenge in contemporary surface and materials science, in particular when introducing well‐defined functionalities in a reversible fashion. Reprogrammable, adaptable and functional interfaces require sophisticated chemistries to precisely equip them with specific functionalities having tailored properties. In the last decade, reversible chemistries—both covalent and noncovalent—have paved the way to precision functionalize 2 or 3D structures that provide both spatial and temporal control. A critical literature assessment reveals that methodologies for writing and erasing substrates exist, yet are still far from reaching their full potential. It is thus critical to assess the current status and to identify avenues to overcome the existing limitations. Herein, the current state‐of‐the‐art in the field of reversible chemistry on surfaces is surveyed, while concomitantly identifying the challenges—not only synthetic but also in current surface characterization methods. The potential within reversible chemistry on surfaces to function as true writeable memories devices is identified, and the latest developments in readout technologies are discussed. Finally, we explore how spatial and temporal control over reversible, light‐induced chemistries has the potential to drive the future of functional interface design, especially when combined with powerful laser lithographic applications.     

Mechanical Behavior of Particle Reinforced Metal Matrix Composites

Metal matrix composites provide significantly enhanced properties — like higher strength, stiffness and weight savings — in comparison to conventional monolithic materials. Particle reinforced MMCs are attractive due to their cost‐effectiveness, isotropic properties, and their ability to be processed using similar technology used for monolithic materials. This review captures the salient features of experimental as well as analytical and computational characterization of the mechanical behavior of MMCs. The main focus is on wrought particulate reinforced light alloy matrix systems, with a particular emphasis on tensile, creep, and fatigue behavior.     

Photoluminescence Architectures for Disease Diagnosis: From Graphene to Thin‐Layer Transition Metal Dichalcogenides and Oxides

Ever since the discovery of graphene, increasing efforts have been devoted to the use of this stellar material as well as the development of other graphene‐like materials such as thin‐layer transition metal dichalcogenides and oxides (TMD/Os) for a variety of applications. Because of their large surface area and unique optical properties, these two‐dimensional materials with a size ranging from the micro‐ to the nanoscale have been employed as the substrate to construct photoluminescence architectures for disease diagnosis as well as theranostics. These architectures are built through the simple self‐assembly of labeled biomolecular probes with the substrate material, leading to signal quenching. Upon the specific interaction of the architecture with a target biomarker, the signal can be spontaneously restored in a reversible manner. Meanwhile, by co‐loading therapeutic agents and employing the inherent photo‐thermal properties of the material substrates, a combined disease imaging and therapy (theranostics) can be achieved. This review highlights the latest advances in the construction and application of graphene and TMD/O based thin‐layer material composites for single‐target and multiplexed detection of a variety of biomarkers and theranostics. These versatile material architectures, owing to their ease in preparation, low cost and flexibility in functionalization, provide promising tools for both basic biochemical research and clinical applications.     

Microstructural and Nano‐Mechanical Characterisation of Multicomponent Composites Nanocrystalline Matrix

Multicomponent, Ti‐based, in situ formed composites with a nanocrystalline matrix are a promising new type of material for structural applications. The materials exhibit an excellent combination of mechanical properties resulting from the composite microstructure. This paper contains a detailed introduction to such materials and a review of the most recent developments in the specific areas of microstructural and nano‐mechanical characterization.     

Carbon Dots‐in‐Matrix Boosting Intriguing Luminescence Properties and Applications

As a new class of luminescent nanomaterials, carbon dots (CDs) have aroused significant interest because of their fascinating photoluminescence properties and potential applications in biological, optoelectronic, and energy‐related fields. Strikingly, embedding CDs in host matrices endow them with intriguing luminescent properties, in particular, room temperature phosphorescence and thermally activated delayed fluorescence, due to the confinement effect of the host matrix and the H‐bonding interactions between CDs and the matrix. Here, the state‐of‐the‐art strategies for introducing CDs in various host matrices are summarized, such as nanoporous materials, polyvinyl alcohol, polyurethane, potash alum, layered double hydroxides, amorphous silica, etc. The resultant luminescent properties of the composites and their emission mechanisms are discussed. Their applications in bioimaging, drug delivery/release, sensing, and anticounterfeiting are also presented. Finally, current problems and challenges of CDs‐based composites are noted for future development of such luminescent materials.     

Optimization of Microporous Carbon Structures for Lithium–Sulfur Battery Applications in Carbonate‐Based Electrolyte

Developing appropriate sulfur cathode materials in carbonate‐based electrolyte is an important research subject for lithium‐sulfur batteries. Although several microporous carbon materials as host for sulfur reveal the effect, methods for producing microporous carbon are neither easy nor well controllable. Moreover, due to the complexity and limitation of microporous carbon in their fabrication process, there has been rare investigation of influence on electrochemical behavior in the carbonate‐based electrolyte for lithium‐sulfur batteries by tuning different micropore size(0–2 nm) of carbon host. Here, we demonstrate an immediate carbonization process, self‐activation strategy, which can produce microporous carbon for a sulfur host from alkali‐complexes. Besides, by changing different alkali‐ion in the previous complex, the obtained microporous carbon exhibits a major portion of ultramicropore (<0.7 nm, from 54.9% to 25.8%) and it is demonstrated that the micropore structure of the host material plays a vital role in confining sulfur molecule. When evaluated as cathode materials in a carbonate‐based electrolyte for Li‐S batteries, such microporous carbon/sulfur composite can provide high reversible capacity, cycling stability and good rate capability.     

Tough,Self‐Healing Hydrogels Capable of Ultrafast Shape Changing

Achieving multifunctional shape‐changing hydrogels with synergistic and engineered material properties is highly desirable for their expanding applications, yet remains an ongoing challenge. The synergistic design of multiple dynamic chemistries enables new directions for the development of such materials. Herein, a molecular design strategy is proposed based on a hydrogel combining acid–ether hydrogen bonding and imine bonds. This approach utilizes simple and scalable chemistries to produce a doubly dynamic hydrogel network, which features high water uptake, high strength and toughness, excellent fatigue resistance, fast and efficient self‐healing, and superfast, programmable shape changing. Furthermore, deformed shapes can be memorized due to the large thermal hysteresis. This new type of shape‐changing hydrogel is expected to be a key component in future biomedical, tissue, and soft robotic device applications.     

Ultra‐High Pyridinic N‐Doped Porous Carbon Monolith Enabling High‐Capacity K‐Ion Battery Anodes for Both Half‐Cell and Full‐Cell Applications

An ultrahigh pyridinic N‐content‐doped porous carbon monolith is reported, and the content of pyridinic N reaches up to 10.1% in overall material (53.4 ± 0.9% out of 18.9 ± 0.4% N content), being higher than most of previously reported N‐doping carbonaceous materials, which exhibit greatly improved electrochemical performance for potassium storage, especially in term of the high reversible capacity. Remarkably, the pyridinic N‐doped porous carbon monolith (PNCM) electrode exhibits high initial charge capacity of 487 mAh g^?1 at a current density of 20 mA g^?1, which is one of the highest reversible capacities among all carbonaceous anodes for K‐ion batteries. Moreover, the K‐ion full cell is successfully assembled, demonstrating a high practical energy density of 153.5 Wh kg^?1. These results make PNCM promising for practical application in energy storage devices and encourage more investigations on a similar potassium storage system.     

A High‐Capacity O2‐Type Li‐Rich Cathode Material with a Single‐Layer Li2MnO3 Superstructure

A high capacity cathode is the key to the realization of high‐energy‐density lithium‐ion batteries. The anionic oxygen redox induced by activation of the Li₂MnO₃ domain has previously afforded an O3‐type layered Li‐rich material used as the cathode for lithium‐ion batteries with a notably high capacity of 250–300 mAh g^?1. However, its practical application in lithium‐ion batteries has been limited due to electrodes made from this material suffering severe voltage fading and capacity decay during cycling. Here, it is shown that an O2‐type Li‐rich material with a single‐layer Li₂MnO₃ superstructure can deliver an extraordinary reversible capacity of 400 mAh g^?1 (energy density: ≈1360 Wh kg^?1). The activation of a single‐layer Li₂MnO₃ enables stable anionic oxygen redox reactions and leads to a highly reversible charge–discharge cycle. Understanding the high performance will further the development of high‐capacity cathode materials that utilize anionic oxygen redox processes.