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.     

电沉积法制备块体纳米晶材料的研究进展

综述了电沉积法制备块体纳米晶材料的原理;阐述了电流密度、电流波形、有机添加剂等工艺参数对沉积层晶粒尺寸的影响;介绍了直流电沉积、脉冲电沉积、喷射电沉积和复合电沉积等几种常见的电沉积方法;概述了电沉积法制备块体纳米晶材料的国内外研究现状;探讨了电沉积块体纳米晶材料的力学性能、磁学性能、耐蚀性能、热稳定性及其应用前景.     

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.     

The evolution of porosity in bulk nanocrystalline materials during plastic deformation and its effect on the mechanical behavior

Uniaxial compression tests were carried out to completely understand the evolution of porosity in porous bulk nanocrystalline materials, and a new evolution law of porosity under uniaxial compression was proposed. Based on the energy principle, we built a mechanical model to calculate the overall mechanical properties of bulk nanocrystalline materials. The comparison between predicted results and the corresponding experimental data indicates that the established model is capable of describing the plastic mechanical behaviors of porous nanocrystalline materials.     

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.     

Structure and properties of nanocrystalline materials

The present article reviews the current status of research and development on the structure and properties of nanocrystalline materials. Nanocrystalline materials are polycrystalline materials with grain sizes of up to about 100 nm. Because of the extremely small dimensions, a large fraction of the atoms in these materials is located at the grain boundaries, and this confers special attributes. Nanocrystalline materials can be prepared by inert gas-condensation, mechanical alloying, plasma deposition, spray conversion processing, and many other methods. These have been briefly reviewed. A clear picture of the structure of nanocrystalline materials is emerging only now. Whereas the earlier studies reasoned out that the structure of grain boundaries in nanocrystalline materials was quite different from that in coarse-grained materials, recent studies using spectroscopy, high-resolution electron microscopy, and computer simulation techniques showed unambiguously that the structure of the grain boundaries is the same in both nanocrystalline and coarse-grained materials. A critical analysis of this aspect and grain growth is presented. The properties of nanocrystalline materials are very often superior to those of conventional polycrystalline coarse-grained materials. Nanocrystalline materials exhibit increased strength/hardness, enhanced diffusivity, improved ductility/toughness, reduced density, reduced elastic modulus, higher electrical resistivity, increased specific heat, higher thermal expansion coefficient, lower thermal conductivity, and superior soft magnetic properties in comparison to conventional coarse-grained materials. Recent results on these properties, with special emphasis on mechanical properties, have been discussed. New concepts of nanocomposites and nanoglasses are also being investigated with special emphasis on ceramic composites to increase their strength and toughness. Even though no components made of nanocrystalline materials are in use in any application now, there appears to be a great potential for applications in the near future. The extensive investigations in recent years on structure-property correlations in nanocrystalline materials have begun to unravel the complexities of these materials, and paved the way for successful exploitation of the alloy design principles to synthesize better materials than hitherto available.     

Fast diffusion in nanocrystalline ceramics prepared by ball milling

Nanocrystalline materials can show enhanced diffusivity compared to their microcrystalline counterparts due to the large fraction of atoms or ions located in interfacial regions. In the case of ceramics, resulting properties with potential applications are, e.g., fast ionic conductivity, high mechanical creep rate and increased catalytic activity. Different nanocrystalline ceramic materials were prepared by high-energy ball milling of coarse grained source materials. The samples were characterized by XRD, TEM, BET method and IR spectroscopy. These measurements show that the primary crystallites form larger agglomerates with internal interfaces and that the reduction of the crystallite size is accompanied by a structural degradation of the surface zone. An example is the partial amorphization observed for LiBO₂ by IR spectroscopy. The diffusivity and ion conductivity in these materials was studied by NMR relaxation, NMR line shape and impedance spectroscopies. It was possible to discriminate between highly mobile ions in the interfacial regions and immobile ions in the grains. In general diffusion in the nanocrystalline systems was found to be fast compared to that in the corresponding microcrystalline source materials.     

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.     

Phase Stability in Nanostructures

Nanostructured materials provide access to tailor‐made materials properties by microstructural design. Excellent mechanical properties such as high strength or wear resistance are often found in nanocrystalline materials. For magnetic materials, the design of nanostructured composites offers advantages if the structural scales match the intrinsic magnetic length scales. In some cases, as in the new nanocrystalline soft magnetic alloys, the combination of amorphous and nanocrystalline phases is necessary to obtain the desired properties. This rises the question of the limiting size for a stable crystalline structure, especially in contact with an amorphous phase. These considerations, which have been of interest for basic research in the context of the microcrystalline model for amorphous materials, are of technical importance for the optimization of nanostructured composites. Recent model experiments about the stability of thin Fe‐based glass forming alloy films are reviewed. A relationship between phase stability, composition, and interface density has been established. The implications of the results for the design of nanostructured alloy systems are discussed.     

金属纳米块体材料制备加工技术和应用

综述了国内外块状纳米材料的制备技术进展及存在的问题 ,提出了超短时脉冲电流直接晶化法和深过冷直接晶化法两类潜在的块状金属纳米晶制备技术 ,并对今后的研究及发展前景进行了展望。同时对大块纳米材料的性能特点及应用前景做了展望     

FePt Hard Magnets

The FePt alloys have recently attracted considerable attention due to their excellent intrinsic magnetic, chemical and mechanical properties. Their possible usage ranges from permanent magnets for special applications (e.g. in micro‐electro‐mechanical systems, magnetic MEMS, and in aggressive environments) to ultra‐high density magnetic storage media. The article describes general aspects concerning the phase formation and magnetic properties of materials based on the L1₀ FePt phase. Both thin film and bulk approaches are considered. The production of bulk nanocrystalline Fe_100‐xPt_x powders by mechanical alloying and subsequent annealing is described. Various combinations of phases, away from thermodynamic equilibrium, have been obtained using this technique.     

Single-wall carbon nanotubes as attractive toughening agents in alumina-based nanocomposites

The extraordinary mechanical, thermal and electrical properties of carbon nanotubes have prompted intense research into a wide range of applications in structural materials, electronics, chemical processing and energy management. Attempts have been made to develop advanced engineering materials with improved or novel properties through the incorporation of carbon nanotubes in selected matrices (polymers, metals and ceramics). But the use of carbon nanotubes to reinforce ceramic composites has not been very successful; for example, in alumina-based systems only a 24% increase in toughness has been obtained so far. Here we demonstrate their potential use in reinforcing nanocrystalline ceramics. We have fabricated fully dense nanocomposites of single-wall carbon nanotubes with nanocrystalline alumina (Al2O3) matrix at sintering temperatures as low as 1,150 degrees C by spark-plasma sintering. A fracture toughness of 9.7 MPa m 1/2, nearly three times that of pure nanocrystalline alumina, can be achieved.     

Preparation of nanocrystalline high-entropy alloys via cryomilling of cast ingots

The advancement of nanotechnology demands large-scale preparation of nanocrystalline powder of innovative materials. High-entropy alloys (HEAs) exhibit unique properties: mechanical, thermal, magnetic etc., making them potentials candidates for applications in energy, environment and biomaterials etc. Thus, there is a need to develop novel synthesis methods to prepare nanocrystalline high-purity HEAs in large quantity. Conventional mechanical alloying of the multicomponent metallic powder mixture requires larger milling time and it is prone to contaminations and phase transformation. The present investigation reports a unique approach, involving casting followed by cryomilling, leading to formation of nanocrystalline HEAs powder, which are relatively contaminations free with narrow size distribution. Using examples of two FCC and one BCC single-phase HEAs, it has been shown that large-scale nanocrystalline HEAs powder can be prepared after few hours of cryomilling at 123 K. The formation of nanocrystalline HEAs during cryomilling has been discussed using theoretically available approaches.     

Preparation of nanocrystalline Ni–Fe strip via mechanical alloying–compaction–sintering–hot rolling route

Nanocrystalline structures offer opportunity for the development of soft magnetic materials, such as 80 wt% Ni–20 wt% Fe, with superior properties. In recent years, nanocrystalline 80Ni–20Fe (wt%) alloy has been prepared by mechanical alloying of elemental powders. However, retention of nanocrystallinity during consolidation of powder is the key issue to take advantage of improved magnetic properties. In the present work, it has been shown that near-full density bulk nanocrystalline 80Ni–20Fe strip can be prepared via a route consisting of mechanical alloying, cold compaction, sintering, and multi-step unsheathed hot rolling. A crack-free strip of nanocrystalline 80Ni–20Fe, having 99% theoretical density and a grain size of approximately 55 nm, was successfully prepared by sintering and hot rolling of mechanically alloyed powder preforms at 1140 °C. The bulk nanocrystalline 80Ni–20Fe material resulted in a very narrow hysteresis loop indicating a very small hysteresis loss. The present study shows that mechanical alloying–sintering–hot rolling route can be a promising method for producing bulk nanocrystalline materials.     

Structurally Controlled Cellular Architectures for High‐Performance Ultra‐Lightweight Materials

The design and synthesis of cellular structured materials are of both scientific and technological importance since they can impart remarkably improved material properties such as low density, high mechanical strength, and adjustable surface functionality compared to their bulk counterparts. Although reducing the density of porous structures would generally result in reductions in mechanical properties, this challenge can be addressed by introducing a structural hierarchy and using mechanically reinforced constituent materials. Thus, precise control over several design factors in structuring, including the type of constituent, symmetry of architectures, and dimension of the unit cells, is extremely important for maximizing the targeted performance. The feasibility of lightweight materials for advanced applications is broadly explored due to recent advances in synthetic approaches for different types of cellular architectures. Here, an overview of the development of lightweight cellular materials according to the structural interconnectivity and randomness of the internal pores is provided. Starting from a fundamental study on how material density is associated with mechanical performance, the resulting structural and mechanical properties of cellular materials are investigated for potential applications such as energy/mass absorption and electrical and thermal management. Finally, current challenges and perspectives on high‐performance ultra‐lightweight materials potentially implementable by well‐controlled cellular architectures are discussed.     

Study on preparation and mechanical property of nanocrystalline NiAl intermetallic

Nanocrystalline NiAl materials were fabricated using mechanical alloying and hot-pressing sintering technique. The crystal structural and microstructure of milled powders during mechanical alloying, and the microstructure and mechanical properties of bulk NiAl intermetallic were characterized. The results show that B2 ordered nanocrystalline NiAl powders were successfully synthesized by solid-state diffusion via the gradual exothermic reaction mechanism during mechanical alloying. Scanning electron microscope image confirmed that the powder particles were flat and flake shape in the early stage of milling, but changed to a spherical shape with the crystallite size about 30 nm after the milling. After sintering, the crystal structure of nanocrystalline NiAl intermetallic was assigned to B2 order NiAl phase with the average crystallite size about 100 nm. The nanocrystalline NiAl intermetallic exhibited prominent room temperature compressive properties, such as the true ultimate compressive strength and the fracture strain were 2143 MPa and 32.2%, respectively. The appearances of vein-like patterns on the fracture surface of NiAl intermetallic materials indicated that the fracture mechanism could be characterized as ductile fracture. It can be concluded that higher sintering density and nanocrystalline of NiAl intermetallic were benefited for the improvement of mechanical properties.     

Engineering Bulk,Layered, Multicomponent Nanostructures with High Energy Density

The precise control of individual components in multicomponent nanostructures is crucial to realizing their fascinating functionalities for applications in electronics, energy‐conversion devices, and biotechnologies. However, this control remains particularly challenging for bulk, multicomponent nanomaterials because the desired structures of the constitute components often conflict. Herein, a strategy is reported for simultaneously controlling the structural properties of the constituent components in bulk multicomponent nanostructures through layered structural design. The power of this approach is illustrated by generating the desired structures of each constituent in a bulk multicomponent nanomaterial (SmCo + FeCo)/NdFeB, which cannot be attained with existing methods. The resulting nanostructure exhibits a record high energy density (31 MGOe) for this class of bulk nanocomposites composed of both hard and soft magnetic materials, with the soft magnetic fraction exceeding 20 wt%. It is anticipated that other properties beyond magnetism, such as the thermoelectric and mechanical properties, can also be tuned by engineering such layered architectures.     

Sputtered tungsten-based ternary and quaternary layers for nanocrystalline diamond deposition

Many of today's demanding applications require thin-film coatings with high hardness, toughness, and thermal stability. In many cases, coating thickness in the range 2-20 microm and low surface roughness are required. Diamond films meet many of the stated requirements, but their crystalline nature leads to a high surface roughness. Nanocrystalline diamond offers a smoother surface, but significant surface modification of the substrate is necessary for successful nanocrystalline diamond deposition and adhesion. A hybrid hard and tough material may be required for either the desired applications, or as a basis for nanocrystalline diamond film growth. One possibility is a composite system based on carbides or nitrides. Many binary carbides and nitrides offer one or more mentioned properties. By combining these binary compounds in a ternary or quaternary nanocrystalline system, we can tailor the material for a desired combination of properties. Here, we describe the results on the structural and mechanical properties of the coating systems composed of tungsten-chromium-carbide and/or nitride. These WC-Cr-(N) coatings are deposited using magnetron sputtering. The growth of adherent nanocrystalline diamond films by microwave plasma chemical vapor deposition has been demonstrated on these coatings. The WC-Cr-(N) and WC-Cr-(N)-NCD coatings are characterized with atomic force microscopy and SEM, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and nanoindentation.     

Strength weakening by nanocrystals in ceramic materials

A key question in nanomechanics concerns the grain size effects on materials' strength. Correct solution to this question is critical to design and tailor the properties of materials for particular applications. The full map of grain sizes-hardness/yield stress relationship in metals has been built. However, for ceramic materials, the similar studies and understandings are really lacking. Here we employed a novel technique to comparatively study the mechanical features of titanium dioxide (TiO(2)) with different crystallite sizes. On the basis of peak profile analysis of the X-ray diffraction data, we determined yield strength for nanocrystalline and bulk TiO(2). Our results reveal a remarkable reduction in yield strength as the grain size decreases from 30-40 microm to approximately 10 nm, providing the only evidence of a strength weakening by nanocrystals relative to their bulk counterparts. This finding infers an inverse Hall-Petch effect, the first of its kind for ceramic materials, and a dramatic strength weakening after the breakdown of classic Hall-Petch relation below a characteristic grain size.