Polycrystalline hcp metals - an important class of engineering materials - typically exhibit complex plasticity because of a limited number of slip systems. Among these metals, deformation is even more complicated in cobalt as it commonly contains residual fcc phase due to the incomplete martensitic fcc$\rightarrow$hcp transformation upon cooling. In this work, we employ a combination of in-situ (acoustic emission, AE) and ex-situ (scanning electron microscopy, SEM) techniques in order to examine deformation dynamics in pure polycrystalline cobalt varying in grain size and the content of residual fcc phase prepared using systematic thermal treatment and cycling. We reveal that the presence of the fcc phase and special ~71° grain boundaries between different hcp martensite variants brings about higher deformability and strength. The fcc phase provides additional slip systems and also accommodates deformation via the stress-induced fcc$\rightarrow$hcp transformation during loading. On the other hand, special boundaries enhance structural integrity and suppress the formation of critical defects. Both these non-trivial effects can dominate over the influence of grain size, being a traditional microstructural variable. The ex-situ SEM experiments further reveal that the stress-induced fcc$\rightarrow$hcp transformation is sluggish and only partial even at high strains, and it does not give rise to detectable AE signals, unlike in other materials exhibiting martensitic transformation. In turn, these insights into cobalt plasticity provide new avenues for the microstructure and performance optimization towards the desired applications through the modern concept of grain boundary engineering.
We developed the self-assembly of epitaxial submicrometer-sized face-centered-cubic (fcc) Co(111) dots using pulsed laser deposition. The dots display atomically-fl at facets, from which the ratios of surface and interface energies for fcc Co are deduced. Zero- field magnetic structures are investigated with magnetic force and lorentz microscopies, revealing vortex-based flux-closure patterns. A good agreement is found with micromagnetic simulations.
Magnetic properties and bonding analyses of perovskite structure Co$_{4}$N nitride have been investigated within density functional theory using both pseudo potential and all electron methods. In the same time, the structural and magnetic stability of pure cobalt in hexagonal close packed (HCP), face centered cubic (FCC) and body centered cubic (BCC) structures are reviewed. At equilibrium, non-spin polarized (NSP) and spin polarized (SP) calculations of the energy versus volume show that the ground state is ferromagnetic in both materials. HCP-Co is found to be more stable than the cubic ones…
We present the theoretical study of thermodynamical properties of fcc-Cu(001) substrate covered by iron-cobalt monolayer as well as by incomplete iron layer. The effective two-dimensional Heisenberg Hamiltonian is constructed from first principles and properties of exchange interactions are investigated. The Curie temperatures are estimated using the Monte-Carlo (MC) simulations and compared with a simplified approach using the random-phase approximation (RPA) in connection with the virtual-crystal approach (VCA) to treat randomness in exchange integrals. Calculations indicate a weak maximum o…
The hcp-fcc transformation induced in cobalt powder by ball milling at room temperature was studied using the excess Gibbs free energy for the metals, in nanometric form, to calculate the activation energy that the atoms need for the phase transformation to occur. The crystalline component of the nanocrystalline cobalt produced in our laboratory, via ball milling, was analized using the radial distribution function technique. The results suggest that the crystalline component has the same structure as the bulk, contradicting results already reported.
The reactive growth of cobalt germanide on Ge(001) was investigated by means of in-situ x-ray absorption spectroscopy photoemission electron microscopy (XAS-PEEM), micro-illumination low-energy electron diffraction ($μ$-LEED), and ex-situ atomic force microscopy (AFM). At a Co deposition temperature of 670°C, a rich morphology with different island shapes and dimensions is observed, and a correlation between island morphology and stoichiometry is found. Combining XAS-PEEM and $μ$-LEED, we were able to identify a large part of the islands to consist of CoGe$_2$, with many of them having an unus…
Evolution of magnetization behaviour of cobalt film on nano patterned silicon substrate, with film thickness, has been studied. In situ magneto-optical Kerr effect measurements during film deposition allowed us to study genuine thickness dependence of magnetization behaviour, all other parameters like surface topology, deposition conditions remaining invariant. The film exhibits uniaxial magnetic anisotropy, with its magnitude decreasing with increasing film thickness. Analysis shows that anisotropy has contributions from both, i) exchange energy which is volume dependent and, ii) stray dipola…
The effects of growth rate (G_r), deposition temperature (T_d), film thickness (t_F), and substrate induced strain (epsilon) on morphological, crystallographic and magnetic characteristics of equiatomic CoPt epitaxial films synthesized with PLD are investigated. The (001) substrates of MgO, STO and LAO provide different degree of epitaxial strain for growth of the disordered face centered cubic (fcc) and ordered face centered tetragonal (L1_0) phases of CoPt. The films deposited at T_d~600 ^0C on all three substrates are fcc with in-plane magnetization and a narrow hysteresis loop of width~200…
Simultaneously probing the electronic structure and morphology of materials at the nanometer or atomic scale while a chemical reaction proceeds is significant for understanding the underlying reaction mechanisms and optimizing a materials design. This is especially important in the study of nanoparticle catalysts, yet such experiments have rarely been achieved. Utilizing an environmental transmission electron microscope (ETEM) equipped with a differentially pumped gas cell, we are able to conduct nanoscopic imaging and electron energy loss spectroscopy (EELS) in situ for cobalt catalysts under…
Cobalt ferrite ultrathin films with inverse spinel structure are among the best candidates for spin-filtering at room temperature. We have fabricated high-quality epitaxial ultrathin CoFe2O4 layers on Ag(001) following a three-step method: an ultrathin metallic CoFe2 alloy was first grown in coherent epitaxy on the substrate, and then treated twice with O2, first at RT and then during annealing. The epitaxial orientation, the surface, interface and film structure were resolved combining LEED, STM, Auger and in situ GIXRD. A slight tetragonal distortion was observed, that should drive the easy …
The mass density of nanowires is determined using in-situ resonance frequency experiments combined with quasi-static nanotensile tests. Our results reveal a mass density of 7.36 g/cm3 on average which is below the theoretical density of bulk cobalt. Also the density of electrodeposited cobalt nanowires is found to decrease with the aspect ratio. The results are discussed in terms of the measurement accuracy and the microstructure of the nanowires.
Growth of Co film on SiO2 substrates with the surface roughness of 0.5 nm and 1.6 nm has been studied in situ using the magneto-optical Kerr effect (MOKE) and four probe resistivity measurements. In-situ measurements jointly suggest the Volmer-Weber growth process and proceed via a nonmagnetic, superparamagnetic and ferromagnetic phase formation on both substrates. Islands are found to coalesce at film thicknesses of 0.6 nm and at 1.5 nm with continuous film formation around film thicknesses of 1.5 nm and 3.0 nm for smooth and rough substrates, respectively. Ferromagnetic long-range ordering i…
Unexpected Planar Dislocation Boundary Formation in FCC Metals Captured by Dark-Field X-ray Microscopy and Continuum Dislocation Dynamics
Technical University of Denmark（丹麦技术大学）；Purdue University（普渡大学）；European Synchrotron Radiation Facility (ESRF)（欧洲同步辐射装置）；Karlsruhe Institute of Technology (KIT)（卡尔斯鲁厄理工学院）
Paths of tetragonal states between two phases of a material, such as bcc and fcc, are called Bain paths. Two simple Bain paths can be defined in terms of special imposed stresses, one of which applies directly to strained epitaxial films. Each path goes far into the range of nonlinear elasticity and reaches a range of structural parameters in which the structure is inherently unstable. In this paper we identify and analyze the general properties of these paths by density functional theory. Special examples include vanadium, cobalt and copper, and the epitaxial path is used to identify an epita…
We present a high-throughput nanoindentation study of in-situ bending effects on incipient plastic deformation behavior of polycrystalline and single-crystalline pure aluminum and pure copper at ultra-nano depths (<200nm). We find that hardness displays a statistically inverse dependence on in-plane stress for indentation depths smaller than 10nm, and the dependence disappears for larger indentation depths. In addition, plastic noise in the nanoindentation force and displacement displays statistically robust noise features, independently of applied stresses. Our experimental results suggest th…
Gadolinium has long been believed to undergo a high pressure phase transition with a volume collapse around 5%. Theoretical explanations have focused on the idea of electrons transferring from the extended s-orbital to the compact f-orbital. However, experimental measurement has been unable to detect any associated change in the magnetic properties of the f-electrons. Here we resolve this discrepancy by showing that there is no significant volume collapse, beyond what is typical in high pressure phase transformations. We present density functional theory calculations of solid gadolinium under …
(Abridged, full abstract available in the text) The main goal of the study presented in this thesis was to perform in-situ investigations on deformation structures in plastically deformed polycrystalline copper at low degrees (<5%) of tensile deformation. Copper is taken as a model system for pure fcc metals. A novel synchrotron-radiation based technique has been developed. The technique allows for in-situ 3D reciprocal space mapping of reflections from deeply-embedded individual grains in polycrystalline samples during tensile deformation. We have shown that the resulting 3D maps from copper,…
An investigation of possibilities for superconductivity mediated by spin fluctuations in some elementary metals is motivated by the recent discovery of superconductivity in the hcp high-pressure phase of iron. The electronic structure, the electron-phonon coupling ($λ_{ph}$) and the coupling due to spin-fluctuations ($λ_{sf}$) are calculated for different phases and different volumes for four elementary metals. The results show that such possibilities are best for systems near, but on the non-magnetic side of, a magnetic instability. Fcc Ni, which show stable magnetism over a wide pressure ran…
In this work we present a study of the structural properties of Fe$_{100-x}$ Ga$_x$ grown by Molecular Beam Epitaxy on Mg0(100). We combine long range and local/chemically selective X-ray probes (X-ray Diffraction and X-ray absorption spectroscopy) together with real space imaging by means of Transmission Electron Microscopy and surface sensitive $in situ$ Reflected High Energy Electron Diffraction. For substrate temperature $T_s$ below 400 $^o$C we obtain $bcc$ films while, for $x \approx$ 24 and $T_s \geq$ 400$^o$C the nucleation of the $fcc$ phase is observed. For both systems a Ga anticlus…
Metals are important structural materials for transport and the built environment. Low carbon steels can fail through strain localisation due to the role of interstitial solute atoms (such as carbon and nitrogen) interacting with mobile dislocations, and this gives rise to the Portevin-Le Chatelier effect and the formation of Luders bands. In this work, we use in-situ tensile testing and observation with High Angular Resolution Electron Back Scatter Diffraction (HR-EBSD) to explore deformation patterning in two Interstitial Free (IF) steel samples. One of these steels was heat treated to trigg…
The martensitic transformation is a fundamental physical phenomenon at the origin of important industrial applications. However, the underlying microscopic mechanism, which is of critical importance to explain the outstanding mechanical properties of martensitic materials, is still not fully understood. This is because for most martensitic materials the transformation is a fast process that makes in situ studies extremely challenging. Noble solids krypton and xenon undergo a progressive pressure induced fcc to hcp martensitic transition with a very wide coexistence domain. Here, we took advant…
Defects formed under irradiation in the bulk act as additional pinning centers resulting in the well-known effect of radiation-induced hardening. On the other hand, there is a poorly understood but well-established effect of instant and reversible softening of metals subjected to various types of irradiation. This radiation-induced softening (RIS) effect should be taken into account both in the theory of radiation effects and in the engineering approach for technological applications. In the present paper, the RIS is investigated experimentally in polycrystalline technically pure iron (0.048%C…
This study investigates the effect of ZrB$_2$ additions on the microstructure, thermal stability, and thermo-mechanical wear behaviour of polycrystalline diamond. Following high-pressure high-temperature (HPHT) sintering, the ZrB$_2$-PCD material showed a full conversion of the binder phase to cobalt-boride (Co2B and Co$_{23}$B$_6$) phases. In-situ PXRD and TEM vacuum annealing experiments observed that the onset of bulk graphitisation occurred above $1000^{\circ}C$ for the ZrB$_2$-PCD material, compared to $850^{\circ}C$ for the STD-PCD material. The ZrB$_2$-PCD tools showed excellent thermo-…
We utilized synchrotron-based in-situ diffraction and dominant shear deformation to identify, dissect, and quantify the relevant deformation mechanisms in nanocrystalline $\mathrm{Pd}_{90}\mathrm{Au}_{10}$ in the limiting case of grain sizes at or below 10 nm. We could identify lattice and grain boundary elasticity, shear shuffling operating in the core region of grain boundaries, stress driven grain boundary migration, and dislocation shear along lattice planes to contribute, however, with significantly different and nontrivial stress-dependent shares to overall deformation. Regarding lattice…
Misfit-dislocation hierarchy governs sliding of asymmetric non-CSL grain boundaries
Woodruff School of Mechanical Engineering, Georgia Institute of Technology（佐治亚理工学院机械工程学院）；School of Mechanics and Engineering Science, Peking University（北京大学力学与工程科学学院）；Institute of Microstructure and Property of Advanced Materials, Beijing Key Lab of Microstructure and Property of Advanced Materials, Beijing University of Technology（北京工业大学先进材料微结构及性能研究所）
