Influence of grain size distribution on the lattice thermal conductivity of Bi2Te3-Sb2Te3-based nanostructured materials

The change of the lattice thermal conductivity of bulk nanostructured materials based on Bi₂Te₃-Sb₂Te₃ solid solutions with grain size distribution has been studied. These materials have a polycrystalline structure with grain sizes ranging from a few tens of a nanometer to a few micrometers. Large grains may contain inclusions or consist of several smaller parts which can be identified with coherent scattering regions seen in X-ray diffraction. The change of the lattice thermal conductivity mediated by additional scattering by inclusions and grain boundaries has been calculated. This calculation allows for the effect of nanoparticle size distribution. The calculated estimates are compared with the available experimental data.     

Inverse Hall–Petch like behaviour in a mechanically milled nanocrystalline Al5Fe2 intermetallic phase

In the present investigation, the indentation study on the high-energy ball-milled nanocrystalline Al₅Fe₂ intermetallic compound has established the inverse Hall–Petch (IHP) behaviour. The structural characterisation of the milled powder particles by X-ray diffraction (XRD) and transmission electron microscopy has shown the evolution of nanocrystalline phase. Micro-indentation measurements have revealed the increase in hardness with decreasing grain size, reaching to a maximum of 9.0 ± 0.3 GPa up to a grain size of 32 ± 4 nm, followed by a decrease. The decrease in hardness with further refinement, an indication of grain size softening, demonstrates the IHP-like behaviour. The deviation from the Hall–Petch behaviour has been discussed using various models based on the dislocations and grain boundary-mediated processes. From the analysis, it appears that the model based on mesocopic grain boundary sliding phenomena is more appropriate to account for the observed grain size softening.     

Hardness and elastic moduli of high pressure synthesized MoB2 and WB2 compacts

High pressure and high temperature synthesized MoB₂ and WB₂ compacts were investigated using X-ray diffraction, energy dispersive spectroscope, scanning electron microscope, Vickers indentation test and ultrasonic measurements. Experiments showed that both MoB₂ and WB₂ compacts are phase pure and with a grain size of 100–200 nm. Vickers indentation test under a large loading force of 49 N showed that the Vickers hardness of MoB₂ and WB₂ are about 21 and 22 GPa, respectively. The bulk modulus and shear modulus are about 296 GPa, and 190 GPa for MoB₂ and 349 and 200 GPa for WB₂ through ultrasonic measurements. Our results indicate that MoB₂ and WB₂ are both hard materials with a hardness similar to that of tungsten carbide, which is widely used in industry.     

Quick preparation and thermal transport properties of nanostructured β-FeSi2 bulk material

This paper reports that the nanostructured β-FeSi2 bulk materials are prepared by a new synthesis process by combining melt spinning(MS) and subsequent spark plasma sintering(SPS).It investigates the influence of linear speed of the rolling copper wheel,injection pressure and SPS regime on microstructure and phase composition of the rapidly solidified ribbons after MS and bulk production respectively,and discusses the effects of the microstructure on thermal transport properties.There are two crystalline phases(α-Fe2Si5 and ε-FeSi) in the rapidly solidified ribbons;the crystal grains become smaller when the cooling rate increases(the 20 nm minimum crystal of ε-FeSi is obtained).Having been sintered for 1 min above 1123 K and annealed for 5 min at 923 K,the single-phase nanostructured βFeSi2 bulk materials with 200-500 nm grain size and 98% relative density are obtained.The microstructure of β-FeSi2 has great effect on thermal transport properties.With decreasing sintering temperature,the grain size decreases,the thermal conductivity of β-FeSi2 is reduced remarkably.The thermal conductivity of β-FeSi2 decreases notably(reduced 72% at room temperature) in comparison with the β-FeSi2 prepared by traditional casting method.     

Elastic properties of nanostructured materials with layered grain boundary structure

Atomistic calculations of the elastic constants for a bulk nanostructured material that consists of a layered structure where alternating layers meet along high angle grain boundaries and where atoms interact via a Lennard-Jones potential are presented. The calculations of the elastic constants were performed in the frame of homogeneous deformations for a wide range of layer widths ranging from 2.24 up to 74.62 nm. The results showed that the relaxation of the atomic structure affects the elastic constants for the cases where more than 5% of atoms are located in the GB region. Also it was found that the way that external stresses are applied on the system affects the values of the obtained elastic properties, with the elastic constants related to the characteristic directions of the grain boundary being the most affected ones. The findings of this work are of interest for the fabrication methods of nanostructured materials, the measurement methods of their elastic properties as well as multiscale modeling schemes of nanostructured materials.     

A thermally activated dislocation-based constitutive flow model of nanostructured FCC metals involving microstructural evolution

Abstract

Due to their interface and nanoscale effects associated with structural peculiarities of nanostructured, face-centered-cubic (FCC) ultrafine-grained/nanocrystalline (UFG/NC) metals, in particular nanotwinned (NT) metals exhibit unexpected deformation behaviours fundamentally different from their coarse-grained (CG) counterparts. These internal boundaries, including grain boundaries and twin boundaries in UFG/NC metals, strongly interact with dislocations as deformation barriers to enhance the strength and strain rate sensitivity (SRS) of materials on the one hand, and play critical roles in their microstructural evolution as dislocation sources/sinks to sustain plastic deformation on the other. In this work, building on the findings of twin softening and (de)twinning-mediated grain growth/refinement in stretched free-standing NT–Ni foils, a constitutive model based on the thermally activated depinning process of dislocations residing in boundaries has been proposed to predict the steady-state grain size and simulate the plastic flow of NT–Ni, by considering the blocking effects of nanotwins on the absorption of dislocations emitted from boundaries. It is uncovered that the stress ratio (η_stress) of effective-to-internal stress can be taken as a signature to estimate the stability of microstructures during plastic deformation. This model not only reproduces well the plastic flow of the stretched NT–Ni foils as well as reported NT–Cu and the steady-state grain size, but also sheds light on the size-dependent SRS and failure of FCC UFG/NC metals. This theoretical framework offers the opportunity to tune the microstructures in the polycrystalline materials to synthesise high performance engineering materials with high strength and great ductility.     

Grain size effects on microstructural stability and creep behaviour of nanotwinned Ni free-standing foils at room temperature

Creep tests were performed on the high stacking fault energy (SFE) nanotwinned (NT) Ni free-standing foils with nearly the same twin thickness at room temperature (RT) to investigate the effects of grain size and loading rate on their microstructural stability and creep behaviour. The grain growth mediated by the twinning/detwinning mechanism at low applied stresses (<800 MPa) and grain refinement via the detwinning mechanism at high applied stresses (>800 MPa) were uncovered in the present NT-Ni foils during RT creep, both of which are attributed to the interactions between dislocations and boundaries. It appears that a higher initial dislocation density leads to a faster primary creep strain rate and a slower steady-state creep strain rate. Unlike the non-twinned metals in which grain growth often enhances the creep strain rate, the twinning/detwinning-mediated grain growth process unexpectedly lowers the steady-state creep strain rate, whereas the detwinning-mediated grain refinement process accelerates the creep strain rate in the studied NT-Ni foils. A modified phase-mixture model combined with Arrhenius laws is put forward to predict the scaling behaviour between the creep strain rate and the applied stress, which also predicts the transition from grain growth-reduced to grain refinement-enhanced steady-state creep strain rate at a critical applied stress. Our findings not only provide deeper insights into the grain size effect on the mechanical behaviour of nanostructured metals with high SFE, but also benefit the microstructure sensitive design of NT metallic materials.     

SEM and TEM analysis of composite of ZrO2-Ti system

3Y-ZrO₂-Ti composites obtained by slip casting method were studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Moreover, the Vickers hardness was measured. The experiments show the complex microstructure of composites. The tetragonal zirconium dioxide (t-ZrO₂) and monoclinic zirconium dioxide (m-ZrO₂) as a composite matrix were detected at XRD analysis. SEM observations revealed that Ti -rich phase are uniform distributed in composites. Moreover, the large and very fine precipitations were found. The very fine Ti rich precipitations were located at ZrO₂ grain boundaries as well as in the triple-points. TEM experiments confirmed that in the sintered composites 3Y-ZrO₂ – 10%Ti the uniaxial ZrO₂ grains (100–600 nm), fine monoclinic martensitic plates and fine round monoclinic particles (20–40 nm) of ZrTiO₂ phase were exist. The complex microstructures of 3Y-ZrO₂-Ti composites have a high hardness as a result of existing fine ZrTiO₂ and other Ti oxides precipitations.     

Nanocrystalline materials – Current research and future directions

Nanocrystalline materials, with a grain size of typically <100 nm, are a new class of materials with properties vastly different from and often superior to those of the conventional coarse-grained materials. These materials can be synthesized by a number of different techniques and the grain size, morphology, and composition can be controlled by controlling the process parameters. In comparison to the coarse-grained materials, nanocrystalline materials show higher strength and hardness, enhanced diffusivity, and superior soft and hard magnetic properties. Limited quantities of these materials are presently produced and marketed in the US, Canada, and elsewhere. Applications for these materials are being actively explored. The present article discusses the synthesis, structure, thermal stability, properties, and potential applications of nanocrystalline materials. This revised version was published online in July 2006 with corrections to the Cover Date.     

Plastic deformation behaviour of layer-grained silver polycrystalline from atomistic simulation

Two types of nanocrystalline polycrystalline silver models in bulk, film and nanowire forms were constructed with layer-grained or equiaxed grain morphologies and average grain sizes of ~7.8 and ~14.7 nm. Uniaxial tensile deformation was performed to investigate the effect of grain morphology and free surface on the plastic deformation behaviour under the strain rate of 5 × 10⁸ and 10⁷ s^?1 at 0.1 K. Grain Boundary (GB) orientation and dimensions in layer-grained morphology promoted the formation of sessile dislocation structures. Some dislocations interacted with each other and some dislocations got obstructed by stacking faults. However, the resulting configurations did not last long enough to cause strain hardening. Strain softening was observed in all models except for the layer-grained models in bulk form, where steady plastic flow was observed after yield. The location and orientation of free surfaces with respect to GBs imposed geometric constraints on the deformation mechanisms (GB sliding and formation of sessile dislocations) which produced asymmetric stress states that influenced the elastic as well as plastic response of the material. The yield stress and flow stress were much smaller at lower strain rate simulations. The proportion of perfect dislocations increased as the strain rate decreased from 5 × 10⁸ to 10⁷ s^?1 due to the decrease of applied stress. Dislocations were mainly emitted from grain boundaries or triple junctions at both high and low strain rate deformations. These results provided insights into the understanding of layer-grained nanocrystalline materials and the synthesis of materials with both high strength and ductility.     

晶体相场法模拟纳米晶材料反霍尔-佩奇效应的微观变形机理

采用晶体相场模型模拟获得了平均晶粒尺寸从11.61–31.32 nm的纳米晶组织, 研究了单向拉伸过程纳米晶组织的强化规律的微观变形机理. 模拟结果表明: 晶粒转动、晶界迁移等晶间变形行为是纳米晶材料的主要微观变形方式, 纳米晶尺寸减小, 有利于晶粒转动, 使屈服强度降低, 显示出反霍尔-佩奇效应.当纳米晶较小时, 变形量超过屈服点达到4%, 位错运动开启, 其对变形的直接贡献有限, 主要通过改变晶界结构而影响变形行为, 位错运动破坏三叉晶界, 引发晶界弯曲, 促进晶界迁移. 随纳米晶增大, 晶粒转动困难, 出现晶界锯齿化并发射位错的现象. 关键词： 晶体相场 纳米晶 反霍尔-佩奇效应 微观变形     

Microstructural evolution and thermal stability of Fe–Zr metastable alloys developed by mechanical alloying followed by annealing

The effect of Zr (up to 1 at.%) addition on the formation of Fe–Zr metastable alloys and their thermal stability were investigated for their possible nuclear applications. Fe–xZr (x = 0.25, 0.5, 1%) alloys were synthesised by mechanical alloying under a high-purity argon atmosphere using stainless steel grinding media in a SPEX 8000M high energy mill. The milling was conducted for 20 h with a ball-to-powder weight ratio of 10:1. The formation of metastable solid solutions after milling was confirmed from the change in the Gibbs free energy analysis as per Miedema’s model. The microstructural characterisation was carried out by analysis of X-ray diffraction, atomic force microscopy and transmission electron microscopy. The effect of Zr on the thermal stability of Fe–Zr alloys was investigated by extensive annealing experiments followed by microstructural analysis and microhardness measurements. The stabilisation was found to occur at 800 °C and thereafter, no significant change in the crystallite size was observed for the samples annealed between 800 and 1200 °C. The supersaturated solid solution, especially 1% Zr alloy, found to be highly stable up to 800 °C and the microhardness value of the same measured to be as high as 8.8 GPa corresponding to a crystallite size of 57 nm. The stabilisation effect has been discussed in the light of both the thermodynamic and kinetic mechanisms and the grain size stabilisation is attributed to the grain boundary segregation of Zr atoms and/or Zener pinning by nanoscale precipitation of the Fe₂Zr phase.     

Study on preparation and properties of molybdenum alloys reinforced by nano-sized ZrO<Subscript>2</Subscript> particles

The nano-sized ZrO₂-reinforced Mo alloy was prepared by a hydrothermal method and a subsequent powder metallurgy process. During the hydrothermal process, the nano-sized ZrO₂ particles were added into the Mo powder via the hydrothermal synthesis. The grain size of Mo powder decreases obviously with the addition of ZrO₂ particles, and the fine-grain sintered structure is obtained correspondingly due to hereditation. In addition to a few of nano-sized ZrO₂ particles in grain boundaries or sub-boundaries, most are dispersed in grains. The tensile strength and yield strength have been increased by 32.33 and 53.76 %.     

Different conduction behaviors of grain boundaries in SiO2-containing 8YSZ and CGO20 electrolytes

Both doped zirconia and ceria have been widely recognized as promising electrolytes in solid oxide fuel cells (SOFC). Total conductivity is an important parameter to evaluate solid electrolytes. It is well know that the contribution to the total conductivity by grain boundaries is especially pronounced for SiO₂-contaminated electrolytes. In this study, we report on the different conduction behaviors of grain boundaries (GB) found in SiO₂-containing (impure) 8YSZ (8 mol% Y₂O₃-doped ZrO₂) and CGO20 (10 mol% Gd₂O₃-doped CeO₂) ceramics. In the grain size range (∼ 0.5–10 μm) studied, the GB conductivity of impure CGO20 ceramics constantly decreases with increasing grain size, in contrast to that observed in impure 8YSZ electrolytes whose GB conductivity increases almost linearly with grain size. It is also found that the variation in GB conductivity versus grain size is different from case to case, depending on the sintering/annealing conditions used to fabricate the ceramics. Two mechanisms were proposed to explain the GB behaviors of the impure 8YSZ and CGO20 ceramics. For doped ceria, the GB phases are supposed to be inert, which do not react with or dissolve into the matrix. Increasing sintering temperature leads to not only grain growth but also change in viscosity and wetting nature of the GB phases. These two factors promote further propagation of the GB phases along the grain boundaries, leading to an increased GB coverage fraction. For doped zirconia, however, the major factor dominating the GB conduction is the further dissolution of SiO₂ into zirconia lattice as a result of increase in sintering temperature or/and time. In addition, we will also evaluate and discuss the validities of the three models that are widely used to analyze the GB conduction in solid electrolytes.     

In situ TEM study of mechanical behaviour of twinned nanoparticles

There is strong interest in studying changes in mechanical properties with reducing grain size. The rational is that consequent dislocation glide cannot be sustained, resulting in an increase in material strength. However, this comes with the cost of a reduction in ductility. It has been shown that coherent twin boundaries in nanostructured Cu improve the ductility to 14% [Lu et al., Science 324 (2009) p. 349]. In this paper, we report for the first time the compression of individual nanoparticles using an in situ force probing holder in the transmission electron microscope. Four types of nanoparticles were tested, three with twin boundaries (decahedra, icosahedra and a single twin) and one free of defects (octahedral). Our results indicate the yield strength of the twinned nanoparticles is between 0.5 and 2.0 GPa. The total malleability for the twinned particles range from 80 to 100%. In addition, experimental results were reproduced by MD simulations of the compression phenomena and suggest that the outstanding mechanical properties are related with partial dislocation multiplication at twin boundaries.     

Formation of nanostructured ω-Al 7 Cu 2 Fe crystalline phase by the ball milling technique

Crystalline ω-Al₇Cu₂Fe bulk samples were prepared by arc furnace and then by means of milling, the average grain size of these samples is reduced to the nanometer scale. The structural and magnetic properties of the nanostructured ω-Al₇Cu₂Fe phase have been studied by X-ray diffraction employing Rietveld method, Mössbauer spectroscopy and vibrating sample magnetometry. The results indicate that the average grain size of the synthesized sample (ω-phase) rapidly decreases from 79 to 12 nm after 5 h of milling. Furthermore, the hyperfine parameters of the nanostructured samples are higher than the values for the bulk ω-phase. Magnetic measurements show a weak ferromagnetic behavior with M _s ?=?0.46 emu.g^???1 for the bulk ω-phase. After the milling process this value increases to M _s ?=?1.50 emu.g^???1 due to the formation and growth of a magnetic interstitial region after reducing the average grain size of the sample.     

Effects of peak current density on the mechanical properties of nanocrystalline Ni-Co alloys produced by pulse electrodeposition

Cobalt content, grain size, microhardness and tensile strength of nanocrystalline Ni-Co deposits produced from a solution containing saccharin and cobalt sulfate at constant electrodeposition conditions (pulse on-time T_on at 1 ms and pulse off-time T_off at 15 ms) but varying the peak current density J_p were investigated. It is found that an increase in J_p makes the deposit Co content lower, colony-like morphology more obvious, grain size smaller, and hardness and tensile strength higher. All of the facts are believed to result from the higher overpotential and nucleation rates caused by the J_p increase. But its further increase could lead to reduction in the hardness and tensile strength. Peak current densities in the range of 100-120 A dm⁻² are recommended for the preparation of nanostructured Ni-Co alloy deposits with grain sizes in the range of 15-20 nm, containing 7-8% Co, possessing hardness of 590-600 kg mm⁻² and tensile strength of 1180-1200 MPa—significantly higher than the strength of pure nickel deposit which is produced by the similar method and gets similar grain size.     

Template growth of vertically aligned carbon nanotubes using self-assembled monolayers of SiO2 particles by Langmuir–Blodgett technique

The thermal stability of nanocrystalline 3R-CuCrO₂ obtaining by hydrothermal method was investigated by annealing treatment, XRD, FT-IR, XPS and TG. The three temperature domains corresponding to thermal stability of 3R-CuCrO₂ nanocrystals (25–400 °C), destabilization of nanocrystalline 3R-CuCrO₂ phase (400–800 °C) and recrystallization of 3R-CuCrO₂ in microcrystalline state over 800 °C, were determined by the specific hydrothermal synthesis conditions. This study has indicated that nanocrystals with delafossite structure synthesized by hydrothermal method exhibit nanocrystalline state up to a reasonably high temperature, about 390 °C, which could be interesting for technical applications and the classical theory of the grain growth.     

Influence of grain boundary state on electrical resistivity of ultrafine grained aluminium

An ultrafine grained (UFG) structure has been obtained in commercial purity Al by high-pressure torsion (HPT). Changes in microhardness and electrical resistivity of the UFG material after annealing at various temperatures within a range of 363–673 K have been investigated in correlation with the microstructure evolution. It has been shown that annealing at 363 K leads to substantial decrease in the electrical resistivity while keeping high microhardness level and approximately the same average grain size. The contributions from the various microstructural units (vacancies, dislocations, grain boundaries (GBs)) to the electrical resistivity were analysed. It was shown for the first time that a non-equilibrium state associated with strain-distorted grain boundary (GB) structure strongly affects electrical resistivity of UFG Al. The resistivity of non-equilibrium GBs in UFG structure formed by HPT was evaluated to be at least 50% higher than the resistivity of the thermally equilibrium GBs in a coarse-grained structure.     

Nanostructured morphology of polymer films prepared by matrix assisted pulsed laser evaporation

As recently illustrated, nanostructured glassy polymer films with exceptional thermal and kinetic stability can be formed via Matrix Assisted Pulsed Laser Evaporation (MAPLE) (Guo et al. in Nat. Mater. 11:337, 2012). Relative to the standard poly(methyl methacrylate) glass formed on cooling at standard rates, glasses prepared by MAPLE can be 40 % less dense and have a 40 K higher glass transition temperature (T _g ). Furthermore, the kinetic stability in the glassy state can be enhanced by 2 orders-of-magnitude. Here, we examine the stability of the structured morphology. We show that nanostructured glasses may be formed even when the substrate is held at temperatures greater than the polymer T _g during deposition. In addition, we discuss the origin of the enhanced stability and the mechanism of nanostructured film formation within the framework of the Zhigilei model. Finally, we compare the nanostructured morphology to the surface morphology of other MAPLE-deposited films in the literature.