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.     

Multiscale Geometric Design Principles Applied to 3D Printed Schwarzites

Schwartzites are 3D porous solids with periodic minimal surfaces having negative Gaussian curvatures and can possess unusual mechanical and electronic properties. The mechanical behavior of primitive and gyroid schwartzite structures across different length scales is investigated after these geometries are 3D printed at centimeter length scales based on molecular models. Molecular dynamics and finite elements simulations are used to gain further understanding on responses of these complex solids under compressive loads and kinetic impact experiments. The results show that these structures hold great promise as high load bearing and impact‐resistant materials due to a unique layered deformation mechanism that emerges in these architectures during loading. Easily scalable techniques such as 3D printing can be used for exploring mechanical behavior of various predicted complex geometrical shapes to build innovative engineered materials with tunable properties.     

Remote, local, and chemical programming of healable multishape memory polymer nanocomposites

We show that the combination of remote, local, and chemical programming of the multishape memory effects offers unparalleled shape and function control in carbon nanotube-Nafion composites. This strategy not only allows the high-fidelity encoding and extraction of designed material shapes at different length scales (macro, micro, and nano) but also enables the reversible tunability of material functions, such as shape memorizability, mechanical properties, surface hydrophobicity, and material resealability, in a single nanocomposite.     

Multiscale Modeling of Crystalline Energetic Materials.

The large discrepancy in length and time scales at which characteristic processes of energetic materials are of relevance pose a major challenge for current simulation techniques. We present a systematic study of crystalline energetic materials of different sensitivity and analyze their properties at different theoretical levels. Information like equilibrium structures, vibrational frequencies, conformational rearrangement and mechanical properties like stiffness and elastic properties can be calculated within the density functional theory (DFT) using different levels of approximations. Dynamical properties are obtained by computations using molecular dynamics at finite temperatures through the use of classical force fields. Effect of defects on structure is studied using classical molecular dynamics methods. Temperature induced reactions at elevated temperatures have been studied using ab initio molecular dynamics method for moderate size crystals of nitroethane. Furthermore, while presenting the state of the art in the study of modeling energetic materials, the current advances in the area as well as the limitations of each methodology are discussed.     

Review of Instrumented Indentation

Instrumented indentation, also known as depth-sensing indentation or nanoindentation, is increasingly being used to probe the mechanical response of materials from metals and ceramics to polymeric and biological materials. The additional levels of control, sensitivity, and data acquisition offered by instrumented indentation systems have resulted in numerous advances in materials science, particularly regarding fundamental mechanisms of mechanical behavior at micrometer and even sub-micrometer length scales. Continued improvements of instrumented indentation testing towards absolute quantification of a wide range of material properties and behavior will require advances in instrument calibration, measurement protocols, and analysis tools and techniques. In this paper, an overview of instrumented indentation is given with regard to current instrument technology and analysis methods. Research efforts at the National Institute of Standards and Technology (NIST) aimed at improving the related measurement science are discussed.     

Not too big,not too small: the appropriate scale

The tools we use at the human scale, whether mechanical, medical or microelectronic, depend on materials for which some other scale of length or time is critical. Often this is the mesoscale, between the scales of engineering and of atomic science. Linking underlying processes to what we handle is sometimes called 'spanning' (or 'bridging') length scales, giving the impression that the mesoscale is a swamp to be crossed without getting mud on our boots. This is misleading: we do not wish to span the mesoscale, but to work at the appropriate scale, and to connect that to our human needs. The appropriate scale need not rule out multiscale computer modelling, in which some supercode integrates relevant scales in one pass, hoping to combine the best of methods for two or more levels. But the reality for such attempts, too often, is that the worst of both regimes are found. Happily, simpler strategies at a judicious scale will often suffice.     

Influence of Structural Principles on the Mechanics of a Biological Fiber‐Based Composite Material with Hierarchical Organization: The Exoskeleton of the Lobster Homarus americanus

The cuticle of the lobster Homarus americanus is a nanocomposite, such as most structural biological materials. It consists of a matrix of chitin‐protein fibers associated with various amounts of crystalline and amorphous calcium carbonate in the rigid parts of the body, and is organized hierarchically at all length scales. One prominent design principle found in the hierarchical structure of such biological fibrous composite materials is the twisted plywood structure. In the lobster cuticle, it is formed by superimposing and gradually rotating planes of parallel aligned chitin‐protein fibers. To adjust the mechanical properties to the requirements on the macroscopic level, the spatial arrangement and the grade of mineralization of the fibers can be modified. A second design principle of lobster cuticle is its honeycomb‐like structure, generated by the well‐developed pore canal system, whose twisted ribbon‐shaped canals penetrate the cuticle perpendicular to its surface. Due to the hierarchical structure, the mechanical properties of the lobster cuticle have to be investigated at different length scales, which is essential for the understanding of the structure–mechanical function relations of mineralized tissues (e.g., potentially also bone and teeth). In order to investigate the influence of the structural principles on the mechanical properties on the macroscopic scale miniaturized tensile, compression, and shear tests were carried out to obtain integral mechanical data. Characterization of the microstructure included scanning electron microscopy (SEM) combined with energy dispersive X‐ray (EDX) measurements.     

Influence of multiwall carbon nanotube functionality and loading on mechanical properties of PMMA/MWCNT bone cements

Poly (methyl methacrylate) (PMMA) bone cement—multi walled carbon nanotube (MWCNT) nanocomposites with weight loadings ranging from 0.1 to 1.0 wt% were prepared. The MWCNTs investigated were unfunctionalised, carboxyl and amine functionalised MWCNTs. Mechanical properties of the resultant nanocomposite cements were characterised as per international standards for acrylic resin cements. These mechanical properties were influenced by the type and wt% loading of MWCNT used. The morphology and degree of dispersion of the MWCNTs in the PMMA matrix at different length scales were examined using field emission scanning electron microscopy. Improvements in mechanical properties were attributed to the MWCNTs arresting/retarding crack propagation through the cement by providing a bridging effect and hindering crack propagation. MWCNTs agglomerations were evident within the cement microstructure, the degree of these agglomerations was dependent on the weight fraction and functionality of MWCNTs incorporated into the cement.     

Miniaturized single-crystalline fcc metals deformed in tension: New insights in size-dependent plasticity

The continuing trend of miniaturizing materials in many modern technological applications has led to a strong demand for understanding the complex mechanical properties of materials at small length scales. This review focuses on the recent understanding of the size-dependent plasticity in single-crystal face-centered cubic (fcc) metals as model systems where microstructural constraints due to grain boundaries can be neglected. The small dimensions of several microns down to some tens of nanometers require sophisticated measurement approaches which are critically revisited. Size effects of the flow stresses are compared for single-crystal “wires” and single-crystalline thin films on compliant or stiff substrates. The interpretation of the results is based on recent insights on dislocation nucleation, mobility, and reactions stemming from in situ transmission electron microscopy studies or discrete dislocation dynamics simulations. Commonalities as well as differences are discussed with the attempt to explain the size effects in tensile testing at small length scales.     

A Modeling Approach Across Length Scales for Progressive Failure Analysis of Woven Composites

This paper presents a multiscale modeling approach for the progressive failure analysis of carbon-fiber-reinforced woven composite materials. Hierarchical models of woven composites at three different length scales (micro, meso, and macro) were developed according to their unique geometrical and material characteristics. A novel strategy of two-way information transfer is developed for the multiscale analysis of woven composites. In this strategy, the macroscopic effective material properties are obtained from property homogenizations at micro and meso scales and the stresses at three length scales are computed with stress amplification method from macroscale to microscale. By means of the two-way information transfer, the micro, meso and macro structural characterizations of composites are carried out so that the micromechanisms of damage and their interactions are successfully investigated in a single macro model. In addition, both the nucleation and growth of damages are tracked during the progressive failure analysis. A continuum damage mechanics (CDM) method is used for post-failure modeling. The material stiffness, tensile strength and damage patterns of an open-hole woven composite laminate are predicted with the proposed multiscale method. The predictions are in good agreement with the experimental results.     

Progress in electron tomography to assess the 3D nanostructure of catalysts

The activity, selectivity and stability of solid catalysts depend critically on the details of their structure at all relevant length scales. Electron tomography (or 3D-TEM) has emerged as a powerful technique for nanostructural characterization. In this review we highlight recent advances in the field of electron tomography for the analysis of solid catalyst. Several examples demonstrate how unique quantitative information can be derived on relevant structural properties such as pore connectivity and corrugation, particle size distributions, and the 3D location of metal nanoparticles in porous oxide or carbon supports. The development of high-resolution imaging and novel reconstruction algorithms is promising to obtain atomically resolved electron tomograms of single catalyst nanoparticles. New reconstruction algorithms allow reconstruction from only a few projections, and hold potential for analyzing beam sensitive samples, as well as for time resolved electron tomography. Element specific or ‘chemical’ electron tomography, using electron energy-loss (EELS) or energy-dispersive X-ray spectroscopy (EDX), is an emerging tool for obtaining both chemical and structural information at nanoscale resolution. The rapid progress in electron tomography over the past few years holds great promise for detailed and quantitative insight into relevant nanostructural properties, thus allowing us to further develop our understanding of the relation between nanostructure and performance for catalysts and related materials.     

Multiscale Soft–Hard Interface Design for Flexible Hybrid Electronics

Emerging next-generation soft electronics will require versatile properties functioning under mechanical compliance, which will involve the use of different types of materials. As a result, control over material interfaces (particularly soft/hard interfaces) has become crucial and is now attracting intensive worldwide research efforts. A series of material and structural interface designs has been devised to improve interfacial adhesion, preventing failure of electromechanical properties under mechanical deformation. Herein, different soft/hard interface design strategies at multiple length scales in the context of flexible hybrid electronics are reviewed. The crucial role of soft ligands and/or polymers in controlling the morphologies of active nanomaterials and stabilizing them is discussed, with a focus on understanding the soft/hard interface at the atomic/molecular scale. Larger nanoscopic and microscopic levels are also discussed, to scrutinize viable intrinsic and extrinsic interfacial designs with the purpose of promoting adhesion, stretchability, and durability. Furthermore, the macroscopic device/human interface as it relates to real-world applications is analyzed. Finally, a perspective on the current challenges and future opportunities in the development of truly seamlessly integrated soft wearable electronic systems is presented.     

Multiscale composition modulated Ti–Al composite processed by severe plastic deformation

Using severe plastic deformation processes to consolidate and co-deform powder mixtures to make ultrafine grain composites is a very attractive approach because it offers an almost non-limited room for combinations of phases and composite structures. The aim of this work was to investigate the mechanisms operating at different length scales and leading to multiscale structures, namely co-deformation, fragmentation and mechanical mixing. A Ti–Al composite was processed from a Ti–Al powder mixture prepared by ball milling and subsequently deformed by equal channel angular pressing. Microstructures were characterized at all length scales, down to the nanometre, using optical microscopy, scanning electron microscopy and transmission electron microscopy. It was found that the final structure exhibits unique features at various length scales. Chemical heterogeneities at the micron scale are the result of co-deformation, while at the sub-micron scale they result from the fragmentation and necking of the Ti hard phase. Then, at the nanometer scale, intermixing occurred and nanoscaled intermetallic particles were discovered. This work highlights the possibilities offered by all these mechanisms to design ultrafine grain composite structures for optimized properties.     

Hierarchical wood cellulose fiber/epoxy biocomposites – Materials design of fiber porosity and nanostructure

Delignified chemical wood pulp fibers can be designed to have a controlled structure of cellulose fibril aggregates to serve as porous templates in biocomposites with unique properties. The potential of these fibers as reinforcement for an epoxy matrix (EP) was investigated in this work. Networks of porous wood fibers were impregnated with monomeric epoxy and cured. Microscopy images from ultramicrotomed cross sections and tensile fractured surfaces were used to study the distribution of matrix inside and around the fibers – at two different length scales. Mechanical characterization at different relative humidity showed much improved mechanical properties of biocomposites based on epoxy-impregnated fibers and they were rather insensitive to surrounding humidity. Furthermore, the mechanical properties of cellulose-fiber biocomposites were compared with those of cellulose-nanofibril (CNF) composites; strong similarities were found between the two materials. The reasons for this, some limitations and the role of specific surface area of the fiber are discussed.     

Finite thermo-elastic decoupled two-scale analysis

Engineering structures are often characterized by different structural properties, depending on the length scale under consideration. Fiber reinforced composites are determined, eg, by a heterogeneous microstructure, but are sufficiently described by homogeneous characteristics at their macroscopic level. Moreover, different loading situations, eg, of thermal or mechanical nature, require the consideration of multiphysical equilibrium states. The challenging engineering task is the computation of the effective material properties of these different loading scenarios. The contribution at hand introduces a finite thermo-elastic two-scale analysis, where the effective macroscopic material properties are computed in a decoupled manner with respect to the different length scales.     

Ultrasonic guided waves in bone

Recent progress in quantitative ultrasound (QUS) has shown increasing interest toward measuring long bones by ultrasonic guided waves. This technology is widely used in the field of nondestructive testing and evaluation of different waveguide structures. Cortical bone provides such an elastic waveguide and its ability to sustain loading and resist fractures is known to be related to its mechanical properties at different length scales. Because guided waves could yield diverse characterizations of the bone's mechanical properties at the macroscopic level, the method of guided waves has a strong potential over the standardized bone densitometry as a tool for bone assessment. Despite this, development of guided wave methods is challenging, e.g., due to interferences and rnultiparametric inversion problems. This paper discusses the promises and challenges related to bone characterization by ultrasonic guided waves.     

In situ tensile testing of nanofibers by combining atomic force microscopy and scanning electron microscopy

A nanomechanical testing set-up is developed by integrating an atomic force microscope (AFM) for force measurements with a scanning electron microscope (SEM) to provide imaging capabilities. Electrospun nanofibers of polyvinyl alcohol (PVA), nylon-6 and biological mineralized collagen fibrils (MCFs) from antler bone were manipulated and tensile-tested using the AFM-SEM set-up. The complete stress-strain behavior to failure of individual nanofibers was recorded and a diversity of mechanical properties observed, highlighting how this technique is able to elucidate mechanical behavior due to structural composition at nanometer length scales.