Magnetic size growth in nanocrystalline copper ferrite

When nanocrystalline copper ferrite (average grain size D≈6 nm) is subjected to high-energy-milling in air over different periods up to 12 h, we observe both a progressive enhancement of the ferrite's magnetic response and a shifting of its superparamagnetic limit. These are revealed by the shift to higher values of the Mössbauer blocking temperature, the maximum of the zero-field cooled magnetization and the start of the irreversibility between the zero-field and field-cooled magnetization curves, while the saturation magnetization and the mean magnetic moment per particle increase. The X-ray diffraction data show that the spinel improves its crystallinity with the milling, by increasing the grain size up to ≈13 nm and, also, reducing its micro-strain level. After 10 h of milling the copper ferrite stabilizes in its cubic metastable phase.     

Mechanical properties of nanocrystalline copper under thermal load

The material properties of nanocrystallines are known to generally have a strong dependence on their nanoscale morphology, such as the grain size. The Hall-Petch effect states that the mechanical strength of nanocrystalline materials can vary substantially for a wide range of grain sizes; this is attributed to the competition between intergranular and intragranular deformations. We employed classical molecular dynamics simulations to investigate the morphology-dependent mechanical properties of nanocrystalline copper. The degradation of material properties under thermal load was investigated during fast strain rate deformation, particularly for the grain size. Our simulation results showed that the thermal load on the nanocrystalline materials alters the grain-size behavior of the mechanical properties.     

Kinetic constants of abnormal grain growth in nanocrystalline nickel

The grain growth in nanocrystalline nickel with a purity of 99.5 at % during non-isothermal annealing was experimentally investigated using differential scanning calorimetry and transmission electron microscopy. Nanocrystalline nickel was prepared by electrodeposition and had an average grain size of approximately 20 nm. It was shown that, at a temperature corresponding to the calorimetric signal peak, abnormal grain growth occurs with the formation of a bimodal grain microstructure. Calorimeters signals were processed within the Johnson–Mehl–Avrami formalism. This made it possible to determine the exponent of the corresponding equation, the frequency factor, and the activation energy of the grain growth, which was found to be equal to the activation energy of the vacancy migration. The reasons for the abnormal grain growth in nanocrystalline nickel were discussed.     

Linear grain growth kinetics and rotation in nanocrystalline Ni

We report three-dimensional atomistic molecular dynamics studies of grain growth kinetics in nanocrystalline Ni. The results show the grain size increasing linearly with time, contrary to the square root of the time kinetics observed in coarse-grained structures. The average grain boundary energy per unit area decreases simultaneously with the decrease in total grain boundary area associated with grain growth. The average mobility of the boundaries increases as the grain size increases. The results can be explained by a model that considers a size effect in the boundary mobility.     

纳晶铜晶粒尺寸对热导率的影响

用热压烧结法制备得到纳晶铜块体. 用激光法测定了不同温度下制备得到的纳晶铜块体的热导率, 并建立卡皮查热阻模型对样品热导率进行模拟. 通过对比, 模拟结果与实验数据基本一致. 随着热压烧结温度的升高, 纳晶铜晶粒尺寸也随之增大. 在900和700 ℃其热导率分别达到了最大和最小值且所对应的热导率分别为200.63和233.37 W·m^-1·K^-1, 各占粗晶铜块体热导率的53.4%和60.6%. 验证了纳晶铜热导率在一定的晶粒尺寸范围内具有尺寸效应, 随着晶粒尺寸的减小, 热导率逐渐减小.     

Simulated defect growth avalanches during deformation of nanocrystalline copper

In this work we introduce a method to capture the proliferation of material defects that carry inelastic deformation, in microstructures simulated through isobaric–isothermal molecular dynamics. Based on the premise that inelastic dissipation is accompanied by a local temperature rise, our method involves analyzing the response of a chain of Nosé–Hoover thermostats that are coupled to the atomic velocities, while the microstructure deforms under the influence of a ramped external stress. We report results obtained from the uniaxial deformation of two nanocrystalline copper microstructures and show that our analysis allows the dissipative signal of a variety of inelastic events to be effectively unified via an ‘avalanche’ of dissipation. Based on this avalanche, we quantitatively compare dissipation for inelastic deformation under tension vs. compression, observing a significant tension–compression asymmetry in this regard. It is concluded that the present method is useful for discerning critical points that correspond to collective yield and inelastic flow.     

Muon diffusion in nanocrystalline copper

A systematic μSR study on nano‐Cu has demonstrated that the diffusion of μ⁺ in nanocrystalline metals is influenced by both features of the nanostructure, i.e., by the very small grain size and by the comparatively large fraction of grain boundaries. The former feature yields a size effect of the phonon‐assisted muon tunneling, but only at particle diameters below 20 nm. The latter feature, in samples with crystallite sizes above 20 nm diameter, i.e., with bulk diffusional behaviour, establishes a connection between μ⁺ diffusion coefficient and particle size: if one of these quantities is known, the other could be evaluated. This revised version was published online in August 2006 with corrections to the Cover Date.     

Roles of grain boundary and dislocations at different deformation stages of nanocrystalline copper under tension

The plastic deformation of nanocrystalline copper subjected to tension has been studied using molecular dynamics simulation. The results show that, in the initial stage, the deformation is mainly boundary-mediated in small grains; while in the late stage, the deformation is accommodated by dislocations in large grains. It is also found that the stress-assisted grain growth occurs owing to atomic diffusion and grain boundary migration. These results are consistent with recent experimental observations.     

Cooperative grain boundary sliding in nanocrystalline materials

Superplastic behaviour of microcrystalline materials is now believed to be controlled by cooperative grain boundary sliding (CGBS). An increasing role of grain boundary mediated plasticity with decreasing grain size down to the nanoscale was predicted leading to the prospect of enhanced superplasticity in nanocrystalline materials. Nevertheless, materials with nanosized grains have revealed a significant decrease in plasticity contrary to theoretical prediction. Direct evidence of CGBS in nanocrystalline Ni₃Al alloy from SEM surface analysis and in-situ TEM tensile testing was detected, confirming one similarity in the rheology of deformation processes between micro- and nanomaterials. Thus, differences in deformation behaviour of materials at these two length scales are related to the probability of sliding surface formation, sliding distance and related accommodation mechanisms.     

Mechanism of film growth of pulsed electrodeposition of nanocrystalline copper in presence of thiourea

This article reports the effect of addition of small amount of thiourea on mechanism of film growth, levelling and grain refinement of pulsed electrodeposition of nanocrystalline copper on stainless steel substrate using simple aqueous acidic copper sulphate solution prepared from 0.25 M CuSO₄·5H₂O and 0.5 M H₂SO₄. The amount of thiourea used in the electrolyte is 0 and 36 mg/l. The results indicate the change in morphology of the deposits with addition of thiourea leading to dendrite free copper deposits. The growth mechanism of the copper deposition is found to change from Volmer–Weber type to Frank-Vander Merwe type making the deposits smoother when deposited with thiourea addition. A small amount (36 mg/l) of thiourea addition leads to decrease in the average grain size of copper from 1160 nm to 14 nm. The results clearly reveal the formation of nanocrystalline copper by addition of thiourea with three orders of magnitude reduction in grain size as compared to the sample deposited without thiourea. Preferential segregation of sulphur (present in thiourea) along the grain boundaries of nanocrystalline copper is shown by energy filter imaging using ultra high resolution transmission electron microscope (TEM), thereby restricting the growth of copper grains during pulsed electrodeposition.     

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.     

Low-temperature plasticity in nanocrystalline titanium and copper

The stress-strain compressive curves, temperature dependences of the yield stress, and small-inelastic-strain rate spectra of coarse-grained and ultrafine-grained (produced by equal-channel angular pressing) titanium and copper are compared in the temperature range 4.2–300 K. As the temperature decreases, copper undergoes mainly strain hardening and titanium undergoes thermal hardening. The temperature dependences of the yield stress of titanium and copper have specific features which correlate with the behavior of their small-inelastic-strain rate spectra. Under the same loading conditions, the rate of microplastic deformation of ultrafine-grained titanium is lower than that of coarse-grained titanium and the rate peaks shift toward high temperatures. The deformation activation volumes of titanium samples differing in terms of their grain size are (10–35)b ³, where b is the Burgers vector magnitude. The dependences of the yield stress on the grain size at various temperatures are satisfactorily described by the Hall-Petch relation.     

Surface magnetism of nanocrystalline copper monoxide

The effect of the surface on the magnetic susceptibility of nanopowders of the CuO semiconducting antiferromagnet was studied. Single-phase nanopowders with nanoparticles 15, 45, and 60 nm in size were prepared through copper vapor condensation in an argon environment, with subsequent oxidation of the copper. The temperature dependences of the magnetic susceptibility of the nanopowders differ qualitatively from the χ (T) relations for bulk samples. In the region 80≤T≤600 K, the magnetic susceptibility of nanopowders is inversely proportional to temperature and is described by the sum of contributions due to the bulk part of CuO and to the Cu²⁺ paramagnetic ions localized in surface layers. The paramagnetic contribution to the total susceptibility is shown to increase with decreasing particle size and sample density. A comparison of the χ (T) relations is made for nanopowders and for a dense CuO nanoceramic with grain size 5≤d≤100 nm prepared using the shock wave technique.     

Study on the effect of temperature rise on grain refining during fabrication of nanocrystalline copper under explosive loading

Nanocrystalline (NC) copper was fabricated by severe plastic deformation of coarse-grained copper at a high strain rate under explosive loading. The feasibility of grain refinement under different explosive loading and the influence of overall temperature rise on grain refinement under impact compression were studied in this paper. The calculation model for the macroscopic temperature rise was established according to the adiabatic shock compression theory. The calculation model for coarse-grained copper was established by the Voronoi method and the microscopic temperature rise resulted from severe plastic deformation of grains was calculated by ANSYS/ls-dyna finite element software. The results show that it is feasible to fabricate NC copper by explosively dynamic deformation of coarse-grained copper and the average grain size of the NC copper can be controlled between 200～400 nm. The whole temperature rise would increase with the increasing explosive thickness. Ammonium nitrate fuel oil explosive was adopted and five different thicknesses of the explosive, which are 20 mm, 25 mm, 30 mm, 35 mm, 45 mm, respectively, with the same diameter using 20 mm to the fly plate were adopted. The maximum macro and micro temperature rise is up to 532.4 K, 143.4 K, respectively, which has no great effect on grain refinement due to the whole temperature rise that is lower than grain growth temperature according to the high pressure melting theory.     

Effect of temperature-strain-rate conditions on grain growth upon heating copper and iron

Stability upon heating an ultrafine structure with high-angle boundaries obtained by shear deformation under pressure depends on the mechanism of its formation (dynamic recrystallization or work hardening) determined by the temperature-rate conditions of plastic deformation. Dynamic recrystallization does not allow attainment of a thermally stable structure.     

High-frequency vibrational properties of metallic nanocrystalline grain boundaries

The high-frequency phonon properties of a computer generated nanocrystalline (nc) fcc Ni with a mean grain size of 5 nm are investigated by directly calculating the on-site phonon Green's function using a recursion technique based on a continued fraction representation. It is found that the high-frequency tail, observed in both experiment and previous simulation work, arises primarily from spatially confined vibrational modes forming within the nc grain boundary regions.     

High-rate deformation of nanocrystalline iron and copper

Stress–strain curves are recorded during a high-speed impact and slow loading for nanocrystalline and coarse-grained iron and copper. The strain-rate sensitivity is determined as a function of the grain size and the strain. It is shown that the well-known difference between the variations of the strain-rate sensitivity of the yield strength with the grain size in fcc and bcc metals can be extended to other strain dependences: the strain-rate sensitivity of flow stresses in iron decreases with increasing strain, and that in copper increases. This difference also manifests itself in different slopes of the dependence of the strain-rate sensitivity on the grain size when the strain changes.     

Emission of partial dislocations by grain boundaries in nanocrystalline metals

A theoretical model is proposed to describe the emission of partial dislocations by grain boundaries in nanocrystalline materials during plastic deformation. Partial dislocations are assumed to be emitted during the motion of grain-boundary disclinations, which are carriers of rotational plastic deformation. The ranges of the parameters of a defect structure in which the emission of partial dislocations by grain boundaries in nanocrystalline metals are energetically favorable are calculated. It is shown that, as the size of a grain decreases, the emission of partial dislocations by its boundary becomes more favorable as compared to the emission of perfect lattice dislocations.     

Dislocation-disclination models of grain boundary migration in ultrathin nanocrystalline films

The dislocation-disclination models describing the athermal migration of grain boundaries in stretched ultrathin nanocrystalline films have been proposed. The cases where the grain boundary emerges on a free surface of the film or is located in its central region have been considered. The changes in the total energy of the system due to the migration of the grain boundary have been calculated, the critical stresses of the onset of migration and the transition from a stable migration to an unstable migration have been determined, and the equilibrium positions of the grain boundary have been found. The dependences of the calculated parameters on the length, the misorientation angle, the position, and the orientation of the grain boundary in the film, as well as on the film thickness, have been investigated. It has been shown that the critical stresses responsible for the onset of migration of the grain boundary and its transition to an unstable regime decrease with a decrease in the thickness of the film. The critical stresses determining the transition from the stable migration to the unstable migration decrease with an increase in the grain size. The closer is the grain boundary to the surface of the film, the more pronounced is the tendency of the grain boundary toward migration.