The influence of grain size and texture on the Young's modulus of nanocrystalline nickel and nickel–iron alloys

Hardness and Young's modulus were measured by nanoindentation on a series of electrodeposited nanocrystalline nickel and nickel–iron alloys. Hardness values showed a transition from regular to inverse Hall–Petch behaviour, consistent with previous studies. There was no significant influence of grain size on the Young's modulus of nanocrystalline nickel and nickel–iron alloys with grain sizes greater than 20?nm. The Young's modulus values for nanocrystalline nickel and nickel–iron alloys for grain sizes less than 20?nm were slightly reduced when compared to their conventional (randomly oriented) polycrystalline counterparts. The observed trend with decreasing grain size was found to be consistent with composite model predictions that consider the influence of intercrystalline defects. However, there was some notable variability of the measured values when compared to the model predictions. Three theoretical relationships were used to characterise the anisotropic elastic behaviour of these materials. As a result, texture was also considered to have an influence on the measured Young's modulus and used to explain some of the observed variability for the entire grain size range (9.8–81?nm).     

Grain Boundary Diffusion and Mechanisms of Creep of Nanostructured Metals

Comparative investigations of diffusion in coarse-grained (d = 20 μm), nanocrystalline (d = 0.04 μm) and nanostructured nickel (d = 0.3 μm) have been carried out in a temperature interval of 0.2–0.3 melting temperature. The reasons for difference of parameters of copper grain-boundary diffusion in the above materials are discussed. The effect exerted by grain boundary state and grain boundary diffusion fluxes of impurity on creep mechanisms of nanostructured nickel and copper in the temperature interval of 373–473 K have been studied. Significant change in the apparent creep activation energy under copper grain boundary diffusion fluxes is described as a consequence of different contribution of grain boundary sliding to overall deformation.     

Hardening and thermal stability of nanocrystalline AlMg4.8 powder

Ball milled nanocrystalline AlMg4.8 powder was investigated in terms of hardening and thermal stability. The validity of the Hall–Petch relation was confirmed down to the minimum grain size of ～44 nm. Prolonged milling in the range of the minimum grain size still increased the hardness. This development is discussed in terms of contamination effects and the influence of full and partial dislocations. Concerning thermal stability, recovery processes occur in the range of 100–230°C, whereas substantial grain growth starts at a temperature of ～250°C. The enthalpy release for recovery was detected to be ～39 J mol^?1 and ～208 J mol^?1 for grain growth. Dynamic strain ageing was indicated by an activation energy for recovery of Q?～?120 kJ mol^?1. The activation energy of grain growth was calculated by means of the Kissinger theory (Q?=?200–210 kJ mol^?1) and using the results of static grain growth (Q?=?204 kJ mol^?1).     

Effect of High-Temperature Structure and Diffusion on Grain-Boundary Diffusion Creep in fcc Metals

Molecular dynamics simulations of high-energy twist and tilt bicrystals of fcc palladium reveal a universal, liquid-like, isotropic high-temperature diffusion mechanism, characterized by a rather low self-diffusion activation energy that is independent of the boundary type or misorientation. Medium-energy grain boundaries exhibit the same behavior at the highest temperatures; however, at lower temperatures the diffusion mechanism becomes anisotropic, with a higher, misorientation-dependent activation energy. Our simulations demonstrate that the lower activation energy at elevated temperatures is caused by a structural transition, from a solid boundary structure at low temperatures to a liquid-like structure at high temperatures. We demonstrate that the existence of such a transition has important consequences for diffusion creep in nanocrystalline fcc metals. In particular, our simulations reveal that in the absence of grain growth, nanocrystalline microstructures containing only high-energy grain boundaries exhibit steady-state diffusion creep with a creep rate that agrees quantitatively with that given by the Coble-creep formula. Remarkably, the activation energy for the high-temperature creep rate is the same as that characterizing the universal high-temperature diffusion in high-energy energy bicrystalline grain boundaries.     

Texture evolution and operative mechanisms during large-strain deformation of nanocrystalline nickel

The large-strain deformation of nanocrystalline nickel was investigated at room temperature and cryogenic (liquid N₂) temperature. Deformation mechanisms ranging from grain boundary sliding to slip, operate due to a wide distribution of grain sizes. These mechanisms leave their finger print in the deformation texture evolution during rolling of nanocrystalline nickel. The occurrence and severance of different mechanisms is understood by a thorough characterization of the deformed samples using X-ray diffraction, X-ray texture measurements, electron back-scattered diffraction and transmission electron microscopy. Crystal plasticity-based viscoplastic self-consistent simulations were used to further substantiate the experimental observations. Thus, a comprehensive understanding of deformation behavior of nanocrystalline nickel, which is characterized by simultaneous operation of dislocation-dominated and grain boundary-mediated mechanisms, has been developed.     

Synthesis of carbon-encapsulated nickel nanoparticles

Carbon-encapsulated metal nanoparticles (CEMNs) were obtained by the catalytic decomposition of hydrocarbons (CH₄, C₂H₆, C₂H₄) on nanocrystalline nickel. Nanocrystalline nickel was obtained by precipitation from nickel nitrate solution, followed by calcination and reduction under hydrogen. A small amount of structural promoters (aluminium and calcium oxide) was added to avoid recrystallisation of fine nickel particles at elevated temperatures. Reduction and carburisation of the samples was carried out in a differential reactor with mass control. The rate of decomposition of methane, ethane and ethylene on nanocrystalline nickel was measured and the apparent activation energy of the process was determined. The obtained samples were characterised using the XRD, SEM and HRTEM methods.     

SmCo7纳米晶合金晶粒组织热稳定性的热力学分析与计算机模拟

推导出了单相纳米晶合金的晶界过剩体积与晶粒尺寸之间的定量关系, 建立了纳米晶合金的晶界热力学性质随温度和晶粒尺寸发生变化的确定性函数. 针对SmCo₇纳米晶合金, 通过纳米晶界热力学函数计算和分析, 研究了单相纳米晶合金的晶粒组织热稳定性. 研究表明, 当纳米晶合金的晶粒尺寸小于对应于体系中晶界自由能最大值的临界晶粒尺寸时, 纳米晶组织处于相对稳定的热力学状态; 当纳米晶粒尺寸达到和超过临界尺寸时, 纳米晶组织将发生热力学失稳, 导致不连续的快速晶粒长大. 利用纳米晶合金热力学理论与元胞自动机算法相耦合的模型对SmCo₇纳米晶合金在升温过程中的晶粒长大行为进行了计算机模拟, 模拟结果与纳米晶合金热力学模型的计算预测结果一致, 由此证实了关于纳米晶合金晶粒组织热稳定性的研究结论. 关键词： 纳米晶合金热力学 7纳米晶合金')" href="#">SmCo₇纳米晶合金 热稳定性 计算机模拟     

Curie Transition of NC Nickel by Mechanical Spectroscopy and Magnetization Study

Mechanical spectroscopy measurement is performed to study the internal friction of nanocrystalline （NC） nickel with an average grain size of 23 nm from room temperature to 610 K. An internal friction peak is observed at about 550 K, which corresponds to the Curie transition process of the NC nickel according to the result of magnetization test. Moreover, the fact that the explained by an analytical model Curie temperature of NC nickel is based on the weakening of cohesive lower than that of coarse-grained nickel is energy.     

An analysis of the grain growth kinetics in Mn2O3 nanocrystals

The isothermal grain growth of Mn₂O₃ nanocrystals, prepared by the chemical liquid-phase homogeneous precipitation route, was investigated at various temperatures between 200 and 500 °C for different annealing times. X-ray diffraction patterns and transmission electron micrographs show that the average grain sizes are in the range of 4–50 nm. The grain growth data were analyzed using two different models. The first model, assuming normal grain growth as that in conventional polycrystalline materials, yields large grain growth exponent (n) and extremely low activation energy (Q). Although it can describe the evolution of grain sizes, it fails to give satisfactory physical interpretation of n and Q, both beyond the theoretical predictions. The second model is based on the structural relaxation of the interface component in nanocrystalline materials. In this case, the ordering of distorted interfaces by structural relaxation proceeds with grain growth. This structure relaxation model not only describes the evolutions of grain growth well, but also makes reasonable attribution of the low activation energy to the short-range rearrangement of atoms in the interface region as well. PACS 63.50.+x; 78.30.-j; 81.20.-n     

Resistance of nanocrystalline vis-à-vis microcrystalline Fe–Cr alloys to environmental degradation and challenges to their synthesis

This paper presents a hypothesis and its experimental validation that a nanostructure can bring about dramatic improvements in the oxidation/corrosion resistance of iron–chromium alloys. More specifically, a nanocrystalline Fe–10 wt% Cr alloy was found to undergo oxidation at a rate that was an order of magnitude lower than its microcrystalline counterpart. Importantly, the oxidation resistance of nanocrystalline Fe–10 wt% Cr alloy was comparable with that of the common corrosion-resistant microcrystalline stainless steels (having 18–20 wt% chromium). The findings have the potential of leading to the next generation of oxidation-resistant alloys. However, due to poor thermal stability of nanocrystalline structure, synthesis/processing of such alloys is a challenge. Discs of nanocrystalline Fe–10% Cr alloy were produced by ball-milling of Fe and Cr powders and compaction of the powder without considerable grain growth by processing within a suitable time–temperature window. The paper also presents a theoretical treatise to arrive at the minimum chromium content required for establishing a protective layer of chromium oxide in an Fe–Cr alloy of a given nanometric grain size.     

Investigation of relaxation processes in nanocrystalline cobalt produced by severe plastic deformation

It has been shown that the dependence of the width of X-ray diffraction lines of plastically deformed cobalt on the annealing temperature is described by the exponential function. Characteristic temperature regions corresponding to the processes of recovery and recrystallization have been established. It has been shown that the values of the activation energy of recrystallization determined from the experimental data are comparable with the activation energy of the grain-boundary diffusion in metals. The activation energy for the recovery region is considerably lower than the activation energy of migration of nonequilibrium grain boundaries in nanocrystalline metals. The X-ray diffraction data have been confirmed by the investigations of the microstructure and microhardness.     

Grain growth in ultrafine titanium powders during sintering

Grain growth behaviour of fine (∼3 μm) and attrition milled nanocrystalline (∼32 nm) titanium powers during sintering have been studied. The activation energies of grain growth (Q _g) in fine titanium were found to be 192.9 and 142.4 kJ/mol at lower and higher temperature ranges, respectively. The nanocrystalline titanium showed very low values of Q _g (54.6 kJ/mol) at lower temperatures and it increased to 273.2 kJ/mol at higher temperatures. The constant (n) in nano Ti system was found to have unusually very high values of 6.5–8.2. The grain boundary rotation along with the diffusional processes could be the grain growth mechanism in nanocrystalline and in fine titanium powders.     

Flow stress/strain rate/grain size coupling for fcc nanopolycrystals

A Hall–Petch (H–P)-type dependence is demonstrated for reciprocal activation volume measurements for nanocrystalline and conventional grain size, strengthened Ni and Cu materials, consistent with predictions derived from the dislocation pile-up model. The observed H–P dependence indicates that the shear stress for cross-slip must be involved in the full grain size regime for transmission of plastic flow at the grain boundaries of fcc metals.     

Nanoscale combined reactions: non-equilibrium α-Co formation in nanocrystalline ϶-Co by abnormal grain growth

Electrodeposited nanocrystalline Co offers a relatively unique opportunity to study the interaction of two fundamentally different elementary solid state reactions: grain growth and ε (HCP) to α (FCC) allotropic phase transformation. Samples were isothermally annealed at temperatures above and below the equilibrium transformation temperature (T_εα?=?695?K) and quenched to ambient for subsequent characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Isothermal annealing above 695?K resulted in concurrent grain growth and ε to α transformation. Unexpectedly, however, simultaneous grain growth and ε to α transformation also occurred during isothermal annealing at temperatures as low as 573?K, i.e. 122?K below the expected equilibrium T_εα. It was observed that non-equilibrium α-Co formed within a matrix of nanocrystalline ε-Co via abnormal grain growth, and is therefore fundamentally different from the ε to α transformation typically observed in conventional polycrystalline Co.     

Three-dimensional atomic scale analysis of nanostructured materials

The 3-dimensional atom probe (3DAP) has been used to provide atomic-scale microcharacterisation of a number of nanostructured materials. Grain boundary segregation has been investigated in electrodeposited nanocrystalline nickel and Ni-P. In the nanocrystalline nickel, there was no observable grain boundary segregation in the as-deposited condition. After annealing, carbon and sulphur contamination was found at the boundary of an abnormally-grown grain. In the as-deposited Ni-P alloy, only limited grain boundary segregation of P is seen, but annealing produces significant segregation and the formation of Ni₃P precipitates at grain boundaries. The phase chemistry in a melt-spun amorphous Fe-Si-Cu-Nb-B-Al (FINEMET-type) alloy has also been studied, and the hetereogeneous nucleation of Fe-Si nanocrystals at Cu precipitates shown conclusively. It is found that at early stages of crystallisation, there is only limited partitioning of the Si between the nanocrystals and the amorphous matrix. Atom probe studies of thin layered films have historically been limited by specimen preparation problems, but recent advances have now yielded data on metallic multilayer films. This has allowed atomic-scale measurements of interface chemistry in these films for the first time.     

Grain boundary self-diffusion of tracer <Superscript>18</Superscript>O atoms in nanocrystalline oxide LaMnO<Subscript>3 + δ</Subscript>

Diffusion coefficients of tracer ¹⁸O atoms at boundaries of nanograins of LaMnO_{3 + δ} oxide have been measured in the temperature range of 400–500°C. The samples of the nanocrystalline oxide are prepared with the use of the shockwave loading method. The concentration profile of the tracer atoms after diffusion annealing is measured with the use of the nuclear microanalysis method. The activation energies of the grain boundary diffusion amounts to about 2 eV and the boundary width is ～0.05 nm. The measured coefficients of the grain boundary diffusion at 500°C exceed the corresponding coefficients of the volume diffusion by seven orders of magnitude.     

Diffusion of nickel in single- and polycrystalline Cr2O3

Chromia protective layers are formed on many industrial alloys to prevent corrosion by oxidation. Their role is to limit the inward diffusion of oxygen and the outward diffusion of cations. A number of chromia-forming alloys contain nickel as a component, such as steels, FeNiCr and NiCr alloys. To ascertain if chromia is a barrier to outward diffusion, nickel diffusion in chromia was studied in both single crystals and polycrystals in the temperature range 900–1100°C at an oxygen pressure of 10^?4 atm (argon + 100 ppm O₂). A nickel film of ～35 nm thick was deposited on the chromia surface and, after diffusing treatment, nickel penetration profiles were established by secondary ion mass spectrometry (SIMS). Two diffusion domains appear in polycrystals, the first domain is assigned to bulk diffusion and the second is due to diffusion along grain boundaries. For the bulk diffusion domain and diffusion in single crystals, using a solution of Fick's second law for diffusion from a thick film, bulk diffusion coefficients were determined at 900 and 1000°C. At the higher temperature, a solution of Fick's second law for diffusion from a thin film could be used. For the second domain in polycrystals, Le Claire's model allowed the grain boundary diffusion parameter (αD _gb δ) to be established. Nickel bulk diffusion does not vary significantly according to the microstructure of chromia. The activation energy of grain boundary diffusion is slightly greater than the activation energy of bulk diffusion, probably on account of segregation phenomena. Nickel diffusion was compared with cationic self-diffusion and with literature data on Fe and Mn heterodiffusion in the bulk and along grain boundaries. All results were analyzed in relation to the oxidation process of stainless steel.     

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.     

Grain growth and collective migration of grain boundaries during plastic deformation of nanocrystalline materials

A theoretical model is proposed for the collective migration of two neighboring grain boundaries (GBs) in a nanocrystalline material under applied elastic stress. By analyzing the change in the energy of the system, it is shown that GBs can remain immobile or migrate toward each other depending on the values of the applied shear stress and misorientation angles. The process of GB migration can proceed either in a stable regime, wherein the GBs occupy equilibrium positions corresponding to a minimum of the energy of the system under relatively small applied stress, or in an unstable regime, wherein the motion of GBs under relatively high stress is accompanied by a continuous decrease in the system energy and becomes uncontrollable. The stable migration of GBs leads to a decrease of the grain bounded by them at the cost of growth of the neighbor grains and can result in complete or partial annihilation of the GBs and the collapse of this grain. Unstable migration leads either to annihilation of GBs or to passage of them through each other, which can be considered as the disappearance of the grain and nucleation and growth of a new grain.     

Strong visible PL from the nc-Si thin film by Ni silicide mediated crystallization

We studied the growth of nanocrystalline silicon (nc-Si) thin film exhibiting a strong room temperature photoluminescence (PL) at 1.81–2.003 eV. The amorphous silicon was crystallized by Ni silicide mediated crystallization (Ni SMC) and then Secco-etched to exhibit the PL. The PL peak energy and intensity increase with increasing the metal density on the a-Si because of the reduction in the grain size down to 2 nm. The photoluminescence energy and peak intensity depend strongly on the Secco etch time because the grain size is reduced by etching the grain boundaries.