Soft Supracrystals of Au Nanocrystals with Tunable Mechanical Properties

The elastic properties of highly ordered three‐dimensional colloidal crystals of gold nanocrystals (called supracrystals) are reported. This study is based on the simultaneous growth of two kinds of gold nanocrystal supracrystals that range in size from 5 nm to 8 nm: interfacial supracrystals and precipitated supracrystals. The elastic properties are deduced from nanoindentation measurements performed with an atomic force microscope. The Young's modulus of the interfacial supracrystals, which grow layer‐by‐layer and form well‐defined films, is compared to that of precipitated supracrystals, which are produced by homogeneous growth in solution. For the precipitated supracrystals, characterized by a thickness larger than 1 μm, the Oliver and Pharr model is used to determine the elastic moduli, which are in the gigapascal range and decrease with increasing nanocrystal size. For the interfacial supracrystals, with 300 nm average thickness, a second model (plate model) is applied in addition to the Oliver and Pharr model. These two models confirm independently that the interfacial films are very soft with Young's modulus in the range of 80–240 MPa. This result reveals a totally new feature of nanocrystal solids, never emphasized before. It is shown that these changes in the Young's modulus are related to the supracrystal growth mechanism.     

Emergence of New Mechanical Functionality in Materials via Size Reduction

Julia R. Greer received her S.B. in Chemical Engineering from the Massachusetts Institute of Technology (1997) and a Ph.D. in Materials Science from Stanford University, where she worked on the nanoscale plasticity of gold with W. D. Nix (2005). She also worked at Intel Corporation in Mask Operations (2000–03) and was a post‐doctoral fellow at the Palo Alto Research Center (2005–07), where she worked on organic flexible electronics with R. A. Street. Greer is a recipient of TR‐35, Technology Review's Top Young Innovator award (2008), a NSF CAREER Award (2007), a Gold Materials Research Society Graduate Student Award (2004), and an American Association of University Women Fellowship (2003). Julia joined Caltech's Materials Science department in 2007 where she is developing innovative experimental techniques to assess mechanical properties of nanometer‐sized materials. One such approach involves the fabrication of nanopillars with different initial microstructures and diameters between 25 nm and 1 µm by using focused ion beam and electron‐beam lithography microfabrication. The mechanical response of these pillars is subsequently measured in a custom‐built in situ mechanical deformation instrument, SEMentor, comprising a scanning electron microscope and a nanoindenter. Read our interview with Prof. Greer on MaterialsViews.com

     

In Situ Study of Size and Temperature Dependent Brittle‐to‐Ductile Transition in Single Crystal Silicon

Silicon based micro‐ and nanometer scale devices operating at various temperatures are ubiquitous today. However, thermo‐mechanical properties of silicon at the small scale and their underlying mechanisms remain elusive. The brittle‐to‐ductile transition (BDT) is one such property relevant to these devises. Materials can be brittle or ductile depending on temperature. The BDT occurs over a small temperature range. For bulk silicon, the BDT is about 545 °C. It is speculated that the BDT temperature of silicon may decrease with size at the nanoscale. However, recent experimental and computational studies have provided inconclusive evidence, and are often contradictory. Potential reasons for the controversy might originate from the lack of an in situ methodology that allows variation of both temperature and sample size. This controversy is resolved in the present study by carrying out in situ thermo‐mechanical bending tests on single crystal silicon samples with concurrent control of these two key parameters. It is unambiguously shown that the BDT temperature reduces with sample size. For example, the BDT temperature decreases to 293 °C for a sample size 720 nm. A mechanism‐based model is proposed to interpret the experimental observations.     

Process Pathway Controlled Evolution of Phase and Van‐der‐Waals Epitaxy in In/In2O3 on Graphene Heterostructures

Many applications of 2D materials require deposition of non‐2D metals and metal‐oxides onto the 2D materials. Little is however known about the mechanisms of such non‐2D/2D interfacing, particularly at the atomic scale. Here, atomically resolved scanning transmission electron microscopy (STEM) is used to follow the entire physical vapor deposition (PVD) cycle of application‐relevant non‐2D In/In₂O₃ nanostructures on graphene. First, a “quasi‐in‐situ” approach with indium being in situ evaporated onto graphene in oxygen‐/water‐free ultra‐high‐vacuum (UHV) is employed, followed by STEM imaging without vacuum break and then repeated controlled ambient air exposures and reloading into STEM. This allows stepwise monitoring of the oxidation of specific In particles toward In₂O₃ on graphene. This is then compared with conventional, scalable ex situ In PVD onto graphene in high vacuum (HV) with significant residual oxygen/water traces. The data shows that the process pathway difference of oxygen/water feeding between UHV/ambient and HV fabrication drastically impacts not only non‐2D In/In₂O₃ phase evolution but also In₂O₃/graphene out‐of‐plane texture and in‐plane rotational van‐der‐Waals epitaxy. Since non‐2D/2D heterostructures' properties are intimately linked to their structure and since influences like oxygen/water traces are often hard to control in scalable fabrication, this is a key finding for non‐2D/2D integration process design.     

Highly Conductive Nanocomposites with Three‐Dimensional,Compactly Interconnected Graphene Networks via a Self‐Assembly Process

Polymer‐based materials with high electrical conductivity are of considerable interest because of their wide range of applications. The construction of a 3D, compactly interconnected graphene network can offer a huge increase in the electrical conductivity of polymer composites. However, it is still a great challenge to achieve desirable 3D architectures in the polymer matrix. Here, highly conductive polymer nanocomposites with 3D compactly interconnected graphene networks are obtained using a self‐assembly process. Polystyrene (PS) and ethylene vinyl acetate (EVA) are used as polymer matrixes. The obtained PS composite film with 4.8 vol% graphene shows a high electrical conductivity of 1083.3 S/m, which is superior to that of the graphene composite prepared by a solvent mixing method. The electrical conductivity of the composites is closely related to the compact contact between graphene sheets in the 3D structures and the high reduction level of graphene sheets. The obtained EVA composite films with the 3D graphene structure not only show high electrical conductivity but also exhibit high flexibility. Importantly, the method to fabricate 3D graphene structures in polymer matrix is facile, green, low‐cost, and scalable, providing a universal route for the rational design and engineering of highly conductive polymer composites.     

In Situ Thermolysis of a Ni Salt on Amorphous Carbon and Graphene Oxide Substrates

Understanding the thermal decomposition of metal salt precursors on carbon structures is essential for the controlled synthesis of metal-decorated carbon nanomaterials. Here, the thermolysis of a Ni precursor salt, NiCl₂·6H₂O, on amorphous carbon (a-C) and graphene oxide (GO) substrates is explored using in situ transmission electron microscopy. Thermal decomposition of NiCl₂·6H₂O on GO occurs at higher temperatures and slower kinetics than on a-C substrate. This is correlated to a higher activation barrier for Cl₂ removal calculated by the density functional theory, strong Ni-GO interaction, high-density oxygen functional groups, defects, and weak van der Waals using GO substrate. The thermolysis of NiCl₂·6H₂O proceeds via multistep decomposition stages into the formation of Ni nanoparticles with significant differences in their size and distribution depending on the substrate. Using GO substrates leads to nanoparticles with 500% smaller average sizes and higher thermal stability than a-C substrate. Ni nanoparticles showcase the fcc crystal structure, and no size effect on the stability of the crystal structure is observed. These findings demonstrate the significant role of carbon substrate on nanoparticle formation and growth during the thermolysis of carbon–metal heterostructures. This opens new venues to engineer stable, supported catalysts and new carbon-based sensors and filtering devices.     

Exploring Nanomechanical Behavior of Silicon Nanowires: AFM Bending Versus Nanoindentation

Despite many efforts to advance the understanding of nanowire mechanics, a precise characterization of the mechanical behavior and properties of nanowires is still far from standardization. The primary objective of this work is to suggest the most appropriate testing method for accurately determining the mechanical performance of silicon nanowires. To accomplish this goal, the mechanical properties of silicon nanowires with a radius between 15 and 70 nm (this may be the widest range ever reported in this research field) are systematically explored by performing the two most popular nanomechanical tests, atomic force microscopy (AFM) bending and nanoindentation, on the basis of different analytical models and testing conditions. A variety of nanomechanical experiments lead to the suggestion that AFM bending based on the line tension model is the most appropriate and reliable testing method for mechanical characterization of silicon nanowires. This recommendation is also guided by systematic investigations of the testing environments through finite element simulations. Results are then discussed in terms of the size‐dependency of the mechanical properties; in the examined range of nanowire radius, the elastic modulus is about 185 GPa without showing significant size dependency, whereas the nanowire strength dramatically increases from 2 to 10 GPa as the radius is reduced.     

Magnetically Enhanced Mechanical Stability and Super‐Size Effects in Self‐Assembled Superstructures of Nanocubes

Artificial materials from the self‐assembly of magnetic nanoparticles exhibit extraordinary collective properties; however, to date, the contribution of nanoscale magnetism to the mechanical properties of this class of materials is overlooked. Here, through a combination of Monte Carlo simulations and experimental magnetic measurements, this contribution is shown to be important in self‐assembled superstructures of magnetite nanocubes. By simulating the relaxation of interacting macrospins in the superstructure systems, the relationship between nanoscale magnetism, nanoparticle arrangement, superstructure size, and mechanical stability is established. For all considered systems, a significant enhancement in cohesive energy per nanocube (up to 45%), and thus in mechanical stability, is uncovered from the consideration of magnetism. Magnetic measurements fully support the simulations and confirm the strongly interacting character of the nanocube assembly. The studies also reveal a novel super‐size effect, whereby mechanically destabilization occurs through a decrease in cohesive energy per nanocube as the overall size (number of particles) of the system decreases. The discovery of this effect opens up new possibilities in size‐controlled tuning of superstructure properties, thus contributing to the design of next‐generation self‐assembled materials with simultaneous enhancement of magnetic and mechanical properties.     

反应物量对纳米晶Fe_3Al组织和性能的影响

利用铝热反应熔化方法分别在反应物量为50、100、200g的条件下制备了块体纳米晶Fe3Al材料,通过TEM和XRD研究了材料的晶粒尺寸,并研究了材料室温压缩性能和硬度。结果表明,所制备的材料主要由非晶和纳米晶组织组成,当反应物量增大,部分区域甚至出现微米晶组织。反应物量为50g时Fe3Al材料中非晶较多,不存在微米晶;反应物量为100g时主要以纳米晶为主,非晶数量减少,伴随有少量的微米晶出现;反应物量为200g时,材料以纳米晶为主,微米晶数量较100g时有所增加。随着反应物量的增加,纳米晶相的平均晶粒尺寸增加,屈服强度和硬度呈先增大后减小的趋势。     

Combination of Surface Charge and Size Controls the Cellular Uptake of Functionalized Graphene Sheets

A fundamental issue for biomedical applications of graphene is the correlation between its physicochemical properties and cellular uptake mechanism. However, such studies are challenging due to the intrinsic polydispersity of graphene. In this work, a series of water soluble graphene sheets with the same polymer coverage, density of functional groups, and fluorescence intensity but three different sizes and surface charges are produced. The effect of the latter two factors and their combination on the mechanism of cellular uptake and intracellular pathways of these defined nanosheets is investigated via confocal and Raman microscopies. While positively (? NH₃⁺) and negatively (? OSO₃^?) charged sheets show an energy dependent uptake, their neutral analogs do not show any significant uptake. The cellular uptake efficacy of positively charged graphene sheets is independent of the size and occurs both through phagocytosis and clathrin‐mediated endocytosis pathways. However, cellular uptake efficacy of graphene sheets with negative surface charge strongly depends on the size of the sheets. They cross the membrane mainly through phagocytosis and sulfate‐receptor‐mediated endocytosis. This study demonstrates that the impact of the size of graphene derivatives on their cellular uptake pathways highly depends on their surface charges and vice versa.     

Graphene and Carbon Nanotube Auxetic Rubber Bionic Composites with Negative Variation of the Electrical Resistance and Comparison with Their Nonbionic Counterparts

Microorganism metabolic activity can facilitate the formation of cellular material systems that have unusual mechanical and physical properties. In the living world microorganisms are commonly used for preparing porous food by fermentation; here carbon nanotubes, graphene nanoplatelets, and a mix of them are dispersed in liquid silicone rubber with single‐cell fungi of commercial beer yeast. The fermentation of such microorganisms during the gelling of the silicone matrix results in bionic composites with buckled/collapsed cells that infer, as rationalized with an analytical model and excluded in a abiotic experimental comparison, auxetic properties. During stretching it is found that the Poisson's ratio of such composites changes sign, from negative to positive, and the variation of the electrical resistance is negative. In addition to the conductivity increment, a general increment of the stretchability and damage resistance with respect to the composites prepared by abiotic process is observed. Bionic composites, even if in their infancy, can thus be multifunctional and superior to their traditional/abiotic counterparts.     

Biomimetic Tendrils by Four Dimensional Printing Bimorph Springs with Torsion and Contraction Properties Based on Bio-Compatible Graphene/Silk Fibroin and Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate)

Taking inspiration from plant tendril geometry, in this study, 4D bimorph coiled structures with an internal core of graphene nanoplatelets-modified regenerated silk and an external shell of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) are fabricated by 4D printing. Finite element simulations and experimental tests demonstrate that integrating these biomaterials with different coefficients of thermal expansion results in the temperature induced self-compression and torsion of the structure. The bimorph spring also exhibits reversible contractive actuation after exposure to water environment that paves its exploitation in regenerative medicine, since core materials also have been proven to be biocompatible. Finally, the authors validate their findings with experimental measurements using such springs for temperature-mediated lengthening of an artificial intestine.     

Metals by Micro‐Scale Additive Manufacturing: Comparison of Microstructure and Mechanical Properties

Many emerging applications in microscale engineering rely on the fabrication of 3D architectures in inorganic materials. Small‐scale additive manufacturing (AM) aspires to provide flexible and facile access to these geometries. Yet, the synthesis of device‐grade inorganic materials is still a key challenge toward the implementation of AM in microfabrication. Here, a comprehensive overview of the microstructural and mechanical properties of metals fabricated by most state‐of‐the‐art AM methods that offer a spatial resolution ≤10 μm is presented. Standardized sets of samples are studied by cross‐sectional electron microscopy, nanoindentation, and microcompression. It is shown that current microscale AM techniques synthesize metals with a wide range of microstructures and elastic and plastic properties, including materials of dense and crystalline microstructure with excellent mechanical properties that compare well to those of thin‐film nanocrystalline materials. The large variation in materials' performance can be related to the individual microstructure, which in turn is coupled to the various physico‐chemical principles exploited by the different printing methods. The study provides practical guidelines for users of small‐scale additive methods and establishes a baseline for the future optimization of the properties of printed metallic objects—a significant step toward the potential establishment of AM techniques in microfabrication.     

Self-Standing 3D Hollow Nanoporous SnO2-Modified CuxO Nanotubes with Nanolamellar Metallic Cu Inwalls: A Facile In Situ Synthesis Protocol toward Enhanced Li Storage Properties

SnO₂ is regarded as a prospective anode material candidate for high energy density lithium-ion batteries (LIBs). However, rapid structural degradation and low conductivity always bring about poor cycling stability and electrochemical reversibility, becoming critical dilemmas toward its practical application. To address these issues, herein, a facile multi-step in situ synthesis protocol is developed to tactfully achieve self-standing 3D hollow nanoporous SnO₂-modified Cu_xO nanotubes with nanolamellar metallic Cu inwalls (3D-HNP SnO₂/Cu_xO@n-Cu) via chemical dealloying, heat treatment, electrochemical replacement, and selective etching. The results show that the unique 3D-HNP SnO₂/Cu_xO@n-Cu as a binder-free integrated anode for LIBs exhibits superior Li storage properties with high initial reversible capacity of 3.34 mAh cm⁻² and good cycling stability with 85.6% capacity retention and >99.4% coulombic efficiency after 200 cycles (capacity decay of only 0.002 mAh cm⁻² per cycle). This is mainly attributed to the unique 3D hollow nanoporous configuration design composed of interlinked Cu_xO nanotubes modified by ultrafine SnO₂ nanocrystals (4–10 nm) with two-way mechanical strain cushion and nanolamellar metallic Cu inwalls with boosted electrical conductivity. This work can be expected to offer an original and effective approach for rational design and fabrication of advanced MOx-based anodes toward high-performance LIBs.     

Atomic‐Scale Spectroscopic Imaging of the Extreme‐UV Optical Response of B‐ and N‐Doped Graphene

Substitutional doping of graphene by impurity atoms such as boron and nitrogen, followed by atom‐by‐atom manipulation via scanning transmission electron microscopy, can allow for accurate tailoring of its electronic structure, plasmonic response, and even the creation of single atom devices. Beyond the identification of individual dopant atoms by means of “Z contrast” imaging, spectroscopic characterization is needed to understand the modifications induced in the electronic structure and plasmonic response. Here, atomic scale spectroscopic imaging in the extreme UV‐frequency band is demonstrated. Characteristic and energy‐loss‐dependent contrast changes centered on individual dopant atoms are highlighted. These effects are attributed to local dopant‐induced modifications of the electronic structure and are shown to be in excellent agreement with calculations of the associated densities of states.     

Thickness Dependence of the Mechanical Properties of Free‐Standing Graphene Oxide Papers

Graphene oxide (GO) papers are candidates for structural materials in modern technology due to their high specific strength and stiffness. The relationship between their mechanical properties and structure needs to be systematically investigated before they can be applied to the broad range fields where they have potential. Herein, the mechanical properties of GO papers with various thicknesses (0.5–100 μm) are investigated using bulge and tensile test methods; this includes the Young's modulus, fracture strength, fracture strain, and toughness. The Young's modulus, fracture strength, and toughness are found to decrease with increasing thickness, with the first two exhibiting differences by a factor of four. In contrast, the fracture strain slightly increases with thickness. Transmission electron, scanning electron, and atomic force microscopy indicate that the mechanical properties vary with thickness due to variations in the inner structure and surface morphology, such as crack formation and surface roughness. Thicker GO papers are weaker because they contain more voids that are produced during the fabrication process. Surface wrinkles and residual stress are found to result in increased fracture strain. Determination of this structure–property relationship provide improved guidelines for the use of GO‐based thin‐film materials in mechanical structures.     

三峡工程坝基花岗岩力学性能的微观分析

本文从矿物组成和微结构特征入手，分析了三峡工程坝区花岗岩的力学性能，通过对新鲜岩样，弱风化（下部）岩样，强风化岩样，全风化岩样的研究，认为大部分弱风化（下部）岩样的矿物组成和微观结构上与新鲜岩样差异不是很大，仍然具有较高的力学强度，强风化，全风化岩人样强度极低，应予彻底清除。同时，文章简述了风化对岩石力学性能的影响，认为风化作用的实质是改变了岩石的微结构以及矿物组成乃至化学成分，从而影响了岩石的力     

On the Catalytic Activity of Sn Monomers and Dimers at Graphene Edges and the Synchronized Edge Dependence of Diffusing Atoms in Sn Dimers

In this study, in situ transmission electron microscopy is performed to study the interaction between single (monomer) and paired (dimer) Sn atoms at graphene edges. The results reveal that a single Sn atom can catalyze both the growth and etching of graphene by the addition and removal of C atoms respectively. Additionally, the frequencies of the energetically favorable configurations of an Sn atom at a graphene edge, calculated using density functional theory calculations, are compared with experimental observations and are found to be in good agreement. The remarkable dynamic processes of binary atoms (dimers) are also investigated and is the first such study to the best of the knowledge. Dimer diffusion along the graphene edges depends on the graphene edge termination. Atom pairs (dimers) involving an armchair configuration tend to diffuse with a synchronized shuffling (step-wise shift) action, while dimer diffusion at zigzag edge terminations show a strong propensity to collapse the dimer with each atom diffusing in opposite directions (monomer formation). Moreover, the data reveals the role of C feedstock availability on the choice a single Sn atom makes in terms of graphene growth or etching. This study advances the understanding single atom catalytic activity at graphene edges.