The new trends in fabrication of bulk nanostructured materials by SPD processing

During the past decade, fabrication of bulk nanostructured metals and alloys using severe plastic deformation (SPD) has been evolving as a rapidly advancing direction of nanomaterials science and technology aimed at developing materials with new mechanical and functional properties for advanced applications. The principle of these developments is based on grain refinement down to the nanoscale level via various SPD techniques. This paper is focused on investigation and development of new SPD processing routes enabling fabrication of fully dense bulk nanostructured metals and alloys with a grain size of 40–50 nm and smaller, namely, SPD-consolidation of powders, including nanostructured ones, as well as SPD-induced nanocrystallization of amorphous alloys. We also consider microstructural features of SPD-processed materials that are responsible for enhancement of their properties.     

Unique mechanical properties of nanostructured metals

Recently, it becomes possible to fabricate bulk metals having ultrafine grained or nanocrystalline structures of which grain size is in nano-meter dimensions. One of the promising ways to realize bulk nanostructured metals is severe plastic deformation (SPD) above logarithmic equivalent strain of 4. We have developed an original SPD process, named Accumulative Roll Bonding (ARB) using rolling deformation in principle, and have succeeded in fabricating bulk nanostructured sheets of various kinds of metals and alloys. The ARB process and the nanostructured metals fabricated by the ARB are introduced in this paper. The nanostructured metals sometimes perform quite unique mechanical properties, that is rather surprising compared with conventionally coarse grained materials. The unique properties seem to be attributed to the characteristic structures of the nano-metals full of grain boundaries.     

Production, properties and application prospects of bulk nanostructured materials

Fundamental mechanisms of grain refinement during equal-channel angular pressing (ECAP) and multiple isothermal forging (MIF) are analyzed and compared. Based on this analysis, deformation methods of nanostructuring are classified into severe plastic deformation and mild plastic deformation methods. It is demonstrated that MIF is a versatile method allowing for a production of bulk and sheet nanostructured semi-products with grain size down to 50 nm and applicable to various metals and alloys. Novel mechanical properties of bulk nanostructured materials produced by this method are presented. The ways of their structural and functional applications are discussed.     

Dynamic Plastic Deformation （DPD）： A Novel Technique for Synthesizing Bulk Nanostructured Metals

While some superior properties of nanostructured materials （with structural scales below 100 nm） have attracted numerous interests of material scientists, technique development for synthesizing nanostructured metals and alloys in 3-dimensional （3D） bulk forms is still challenging despite of extensive investigations over decades. Here we report a novel synthesis technique for bulk nanostructured metals based on plastic deformation at high Zener-Hollomon parameters （high strain rates or low temperatures）, i.e., dynamic plastic deformation （DPD）. The basic concept behind this approach will be addressed together with a few examples to demonstrate the capability and characteristics of this method. Perspectives and future developments of this technique will be highlighted.     

Melt Infiltration: an Emerging Technique for the Preparation of Novel Functional Nanostructured Materials

The rapidly expanding toolbox for design and preparation is a major driving force for the advances in nanomaterials science and technology. Melt infiltration originates from the field of ceramic nanomaterials and is based on the infiltration of porous matrices with the melt of an active phase or precursor. In recent years, it has become a technique for the preparation of advanced materials: nanocomposites, pore‐confined nanoparticles, ordered mesoporous and nanostructured materials. Although certain restrictions apply, mostly related to the melting behavior of the infiltrate and its interaction with the matrix, this review illustrates that it is applicable to a wide range of materials, including metals, polymers, ceramics, and metal hydrides and oxides. Melt infiltration provides an alternative to classical gas‐phase and solution‐based preparation methods, facilitating in several cases extended control over the nanostructure of the materials. This review starts with a concise discussion on the physical and chemical principles for melt infiltration, and the practical aspects. In the second part of this contribution, specific examples are discussed of nanostructured functional materials with applications in energy storage and conversion, catalysis, and as optical and structural materials and emerging materials with interesting new physical and chemical properties. Melt infiltration is a useful preparation route for material scientists from different fields, and we hope this review may inspire the search and discovery of novel nanostructured materials.     

Recent advances and remaining challenges of nanostructured materials for hydrogen storage applications

The rapid and extensive development of advanced nanostructures and nanotechnologies has driven a correspondingly rapid growth of research that presents enormous potential for fulfilling the practical requirements of solid state hydrogen storage applications. This article reviews the most recent progress in the development of nanostructured materials for hydrogen storage technology, demonstrating that nanostructures provide a pronounced benefit to applications involving molecular hydrogen storage, chemical hydrogen storage, and as supports for the nanoconfinement of various hydrides. To further optimize hydrogen storage performance, we emphasize the desirability of exploring and developing nanoporous materials with ultrahigh surface areas and the advantageous incorporation of metals and functionalities, nanostructured hydrides with excellent mechanic stabilities and rigid main construction, and nanostructured supports comprised of lightweight components and enhanced hydride loading capacities. In addition to highlighting the conspicuous advantages of nanostructured materials in the field of hydrogen storage, we also discuss the remaining challenges and the directions of emerging research for these materials.     

Structured Porous Materials via Colloidal Crystal Templating: From Inorganic Oxides to Metals

The formation of nanostructured materials by using colloidal crystals as templates is a relatively new but rapidly growing area of materials science. Colloid crystalline templates are three‐dimensional close‐packed crystals of submicrometer spheres, whose long‐ranged ordered structure is replicated in a solid matrix, to yield materials with ordered pores. These materials hold promise for use as photonic crystals, advanced catalysts, and in a variety of other applications. Here we review the wide range of materials that have been made following the original synthesis of structured porous silica. This method has been recently modified to produce porous metals.     

An overview—Functional nanomaterials for lithium rechargeable batteries,supercapacitors, hydrogen storage,and fuel cells

There is tremendous worldwide interest in functional nanostructured materials, which are the advanced nanotechnology materials with internal or external dimensions on the order of nanometers. Their extremely small dimensions make these materials unique and promising for clean energy applications such as lithium ion batteries, supercapacitors, hydrogen storage, fuel cells, and other applications. This paper will highlight the development of new approaches to study the relationships between the structure and the physical, chemical, and electrochemical properties of functional nanostructured materials. The Energy Materials Research Programme at the Institute for Superconducting and Electronic Materials, the University of Wollongong, has been focused on the synthesis, characterization, and applications of functional nanomaterials, including nanoparticles, nanotubes, nanowires, nanoporous materials, and nanocomposites. The emphases are placed on advanced nanotechnology, design, and control of the composition, morphology, nanostructure, and functionality of the nanomaterials, and on the subsequent applications of these materials to areas including lithium ion batteries, supercapacitors, hydrogen storage, and fuel cells.     

Preparation and characterization of rare-earth bulks with controllable nanostructures

The preparation and characterization of pure rare-earth-metal bulks with controllable nanostructures are reported in this paper. A novel 'oxygen-free' in?situ synthesis technique that combines inert-gas condensation with spark plasma sintering (SPS) technology is proposed. Taking into account the special mechanisms of SPS consolidation and the scale effects of nanoparticles, we introduced practical procedures for preparing rare-earth bulks of amorphous, mixed amorphous and nanocrystals, and nanocrystalline microstructures, respectively. Compared with the conventional polycrystalline bulk, these nanostructured bulks exhibit substantially improved physical and mechanical properties. This technique enables comprehensive studies on the microstructures and properties of a large variety of nanostructured metallic materials that are highly reactive in the air.     

Nanostructuring strategies in functional fine-particle synthesis towards resource and energy saving applications

As a low cost and environmentally-benign powder technology, appropriate nanostructuring of fine particles (for example to produce porous, core–shell, hollow, or multicomponent composite structures) has attracted significant attention. Nanostructured fine particles have superior properties, such as high specific surface area, low density, hybrid functionalities, and resistance to weathering. Research into ways of nanostructuring particles for advanced functional materials has progressed rapidly, because these particles offer two great advantages over bulk materials or single component spherical particles: high performance and reduction in the use of expensive raw materials. In particular, the current interest in nanostructured particles focuses on tailoring their inner structure and morphology towards particular practical applications. This article reviews recent research progress on fabrication strategies for nanostructured fine particles. The examples chosen are phosphors, photocatalysts, electrocatalysts, adsorbents and magnetic particles. These fabrication techniques pave the way towards saving both resources and energy in materials production.     

Nanostructured Composite Materials with Improved Deformation Behavior

The recent progress in the development of nanostructured composites is described for Zr‐base multicomponent alloys as a typical example for such materials. These advanced composite materials are attractive candidates for structural as well as functional applications. The combination of high strength with high elastic strain of fully nanocrystalline and glassy alloys renders them quite unique in comparison to conventional (micro‐)crystalline materials. However, one major drawback for their use in engineering applications is the often limited macroscopic plastic deformability, despite the fact that some of these alloys show perfectly elastic‐plastic deformation behavior. To improve the room temperature ductility of either fully nanocrystalline or amorphous alloys, the concept of developing a heterogeneous microstructure combining a glassy or nanostructured matrix with second‐phase particles with a different length‐scale, has recently been employed. This review describes the composition dependent metastable phase formation in the Zr‐(Ti/Nb)‐Cu‐Ni‐Al alloy system, which in turn alters the mechanical properties of the alloys. We emphasize the possibilities to manipulate such composite microstructures in favor of either strength or ductility, or a combination of both, and also discuss the acquired ability to synthesize such in‐situ high‐strength composite microstructures in bulk form through inexpensive processing routes.     

Fast Self-Assembly Dynamics of a β-Sheet Peptide Soft Material

Peptide-based hydrogels are promising biocompatible materials for wound healing, drug delivery, and tissue engineering applications. The physical properties of these nanostructured materials depend strongly on the morphology of the gel network. However, the self-assembly mechanism of the peptides that leads to a distinct network morphology is still a subject of ongoing debate, since complete assembly pathways have not yet been resolved. To unravel the dynamics of the hierarchical self-assembly process of the model β-sheet forming peptide KFE8 (Ac-FKFEFKFE-NH₂)_, high-speed atomic force microscopy (HS-AFM) in liquid is used. It is demonstrated that a fast-growing network, based on small fibrillar aggregates, is formed at a solid–liquid interface, while in bulk solution, a distinct, more prolonged nanotube network emerges from intermediate helical ribbons. Moreover, the transformation between these morphologies has been visualized. It is expected that this new in situ and in real-time methodology will set the path for the in-depth unravelling of the dynamics of other peptide-based self-assembled soft materials, as well as gaining advanced insights into the formation of fibers involved in protein misfolding diseases.     

Revealing the atomistic deformation mechanisms of face-centered cubic nanocrystalline metals with atomic-scale mechanical microscopy: A review

Nanocrystalline metals have many functional and structural applications due to their excellent mechanical properties compared to their coarse-grained counterparts. The atomic-scale understanding of the deformation mechanisms of nanocrystalline metals is important for designing new materials, novel structures and applications. The review presents recent developments in the methods and techniques for in situ deformation mechanism investigations on face-centered-cubic nanocrystalline metals. In the first part, we will briefly introduce some important techniques that have been used for investigating the deformation behaviors of nanomaterials. Then, the size effects and the plasticity behaviors in nanocrystalline metals are discussed as a basis for comparison with the plasticity in bulk materials. In the last part, we show the atomic-scale and time-resolved dynamic deformation processes of nanocrystalline metals using our in-lab developed deformation device.     

Nanoporous Ge electrode as a template for nano-sized ( < 5 nm) Au aggregates

In this paper we present the extremely peculiar electrical properties of nanoporous Ge. A full and accurate electrical characterization showed an unexpected and extremely high concentration of positive carriers. Electrochemical analyses showed that nanoporous Ge has improved charge transfer properties with respect to bulk Ge. The electrode behavior, together with the large surface-to-volume ratio, make nanoporous Ge an efficient nanostructured template for the realization of other porous materials by electrodeposition. The pores were efficiently decorated by Au nanoparticles of diameter as low as 1-5?nm, prepared by electrochemical deposition. These new results demonstrate the potential and efficient use of nanoporous Ge as a nanostructured template for nano-sized Au aggregates, opening the way for the realization of innovative sensor devices.     

Metal Chalcogenide Clusters on the Border between Molecules and Materials

The preparative and materials chemistry of high nuclearity transition metal chalcogenide nanoclusters has been in the focus of our research for many years. These polynuclear metal compounds possess rich photophysical properties and can be understood as intermediates between mononuclear complexes and binary bulk phases. Based on our previous results we discuss herein recent advances in three different areas of cluster research. In the field of copper selenide clusters we present the synthesis of monodisperse, nanostructured α‐Cu₂Se via the thermolysis of well‐defined cluster compounds as well as our approaches in the synthesis of functionalized clusters. In case of silver chalcogenides we established a strategy to synthesis cluster compounds containing several hundreds of silver atoms with the nanoclusters arranging in a closely packed crystal lattice. Finally the presented chalcogenide clusters of the group 12 metals (Zn, Cd, Hg) can be taken as model compounds for corresponding nanoparticles as even the smallest of frameworks display a clear structural relationship to the bulk materials.     

Acoustic Properties of Aerogels: Current Status and Prospects

Noise reduction remains an important priority in the modern society, in particular, for urban areas and highly populated cities. Insulation of buildings and transport systems such as cars, trains, and airplanes has accelerated the need to develop advanced materials. Various porous materials, such as commercially available foams and granular and fibrous materials, are commonly used for sound mitigating applications. In this review, a special class of advanced porous materials, aerogels, is examined, and an overview of the current experimental and theoretical status of their acoustic properties is provided. Aerogels can be composed of inorganic matter, synthetic or natural polymers, as well as organic/inorganic composites and hybrids. Aerogels are highly porous nanostructured materials with a large number of meso- and small macropores; the mechanisms of sound absorption partly differ from those of traditional porous absorbers possessing large macropores. The understanding of the acoustic properties of aerogels is far from being complete, and experimental results remain scattered. It is demonstrated that the structure of the aerogel provides a complex three-dimensional architecture ideally suited for promising high-performance materials for acoustic mitigation systems. This is in addition to the numerous other desirable properties that include low density, low thermal conductivity, and low refractive index.     

制备块体纳米/超细晶材料的大塑性变形技术

综述了采用SPD技术制备块体超细晶(UFG)和纳米晶(NC)材料的几种新方法，如等通道角挤压、高压扭转、多向锻造、多向压缩、板条马氏体冷轧法、累积轧焊法、冷拔、反复弯曲平直法等，分析了采用这些工艺制备的块体纳米材料所共有的微观组织特点。着重阐述了SPD技术的研究进展。     

Synthesis of nanostructured materials using supercritical CO<Subscript>2</Subscript>: Part I. Physical transformations

Nanostructured materials have been attracting increased attention for a wide variety of applications due to their superior properties compared to their bulk counterparts. Current methods to synthesize nanostructured materials have various drawbacks such as difficulties in control of the nanostructure and morphology, excessive use of solvents, abundant energy consumption, and costly purification steps. Supercritical fluids especially supercritical carbon dioxide (scCO₂) is an attractive medium for the synthesis of nanostructured materials due to its favorable properties such as being abundant, inexpensive, non-flammable, non-toxic, and environmentally benign. Furthermore, the thermophysical properties of scCO₂ can be adjusted by changing the processing temperature and pressure. The synthesis of nanostructured materials in scCO₂ can be classified as physical and chemical transformations. In this article, Part I of our review series, synthesis of nanostructured materials using physical transformations is described where scCO₂ functions as a solvent, an anti-solvent or as a solute. The nanostructured materials, which can be synthesized by these techniques include nanoparticles, nanowires, nanofibers, foams, aerogels, and polymer nanocomposites. scCO₂ based processes can also be utilized in the intensification of the conventional processes by elimination of some of the costly purification or separation steps. The fundamental aspects of the processes, which would be beneficial for further development of the technologies, are also reviewed.     

Modification of nanostructured materials for biomedical applications

Adaptation (or incorporation) of nanostructured materials into biomedical devices and systems has been of great interest in recent years. Through the modification of existing nanostructured materials one can control and tailor the properties of such materials in a predictable manner, and impart them with biological properties and functionalities to better suit their integration with biomedical systems. These modified nanostructured materials can bring new and unique capabilities to a variety of biomedical applications ranging from implant engineering and modulated drug delivery, to clinical biosensors and diagnostics. This review describes recent advances of nanostructured materials for biomedical applications. The methods and technologies used to modify nanostructured materials are summarized briefly, while several current interests in biomedical applications for modified and functionalized nanostructured materials are emphasized.     

Nanostructure design for drastic reduction of thermal conductivity while preserving high electrical conductivity

The design and fabrication of nanostructured materials to control both thermal and electrical properties are demonstrated for high-performance thermoelectric conversion. We have focused on silicon (Si) because it is an environmentally friendly and ubiquitous element. High bulk thermal conductivity of Si limits its potential as a thermoelectric material. The thermal conductivity of Si has been reduced by introducing grains, or wires, yet a further reduction is required while retaining a high electrical conductivity. We have designed two different nanostructures for this purpose. One structure is connected Si nanodots (NDs) with the same crystal orientation. The phonons scattering at the interfaces of these NDs occurred and it depended on the ND size. As a result of phonon scattering, the thermal conductivity of this nanostructured material was below/close to the amorphous limit. The other structure is Si films containing epitaxially grown Ge NDs. The Si layer imparted high electrical conductivity, while the Ge NDs served as phonon scattering bodies reducing thermal conductivity drastically. This work gives a methodology for the independent control of electron and phonon transport using nanostructured materials. This can bring the realization of thermoelectric Si-based materials that are compatible with large scale integrated circuit processing technologies.