Structural Evolution during Milling, Annealing, and Rapid Consolidation of Nanocrystalline Fe-10Cr-3Al Powder.
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ABSTRACT: Structural changes during the deformation-induced synthesis of nanocrystalline Fe-10Cr-3Al alloy powder via high-energy ball milling followed by annealing and rapid consolidation by spark plasma sintering were investigated. Reduction in crystallite size was observed during the synthesis, which was associated with the lattice expansion and rise in dislocation density, reflecting the generation of the excess grain boundary interfacial energy and the excess free volume. Subsequent annealing led to the exponential growth of the crystallites with a concomitant drop in the dislocation density. The rapid consolidation of the as-synthesized nanocrystalline alloy powder by the spark plasma sintering, on the other hand, showed only a limited grain growth due to the reduction of processing time for the consolidation by about 95% when compared to annealing at the same temperature.
Project description:The microstructural evolution of Dy₂O₃-TiO₂ powder mixtures during ball milling and post-milled annealing was investigated using XRD, SEM, TEM, and DSC. At high ball-milling rotation speeds, the mixtures were fined, homogenized, nanocrystallized, and later completely amorphized, and the transformation of Dy₂O₃ from the cubic to the monoclinic crystal structure was observed. The amorphous transformation resulted from monoclinic Dy₂O₃, not from cubic Dy₂O₃. However, at low ball-milling rotation speeds, the mixtures were only fined and homogenized. An intermediate phase with a similar crystal structure to that of cubic Dy₂TiO₅ was detected in the amorphous mixtures annealed from 800 to 1000 °C, which was a metastable phase that transformed to orthorhombic Dy₂TiO₅ when the annealing temperature was above 1050 °C. However, at the same annealing temperatures, pyrochlore Dy₂Ti₂O₇ initially formed and subsequently reacted with the remaining Dy₂O₃ to form orthorhombic Dy₂TiO₅ in the homogenous mixtures. The evolutionary mechanism of powder mixtures during ball milling and subsequent annealing was analyzed.
Project description:The microstructural evolution, thermodynamics, and kinetics of Mo (21 wt %) Tm₂O₃ powder mixtures during ball milling were investigated using X-ray diffraction and transmission electron microscopy. Ball milling induced Tm₂O₃ to be decomposed and then dissolved into Mo crystal. After 96 h of ball milling, Tm₂O₃ was dissolved completely and the supersaturated nanocrystalline solid solution of Mo (Tm, O) was obtained. The Mo lattice parameter increased with increasing ball-milling time, opposite for the Mo grain size. The size and lattice parameter of Mo grains was about 8 nm and 0.31564 nm after 96 h of ball milling, respectively. Ball milling induced the elements of Mo, Tm, and O to be distributed uniformly in the ball-milled particles. Based on the semi-experimental theory of Miedema, a thermodynamic model was developed to calculate the driving force of phase evolution. There was no chemical driving force to form a crystal solid solution of Tm atoms in Mo crystal or an amorphous phase because the Gibbs free energy for both processes was higher than zero. For Mo (21 wt %) Tm₂O₃, it was mechanical work, not the negative heat of mixing, which provided the driving force to form a supersaturated nanocrystalline Mo (Tm, O) solid solution.
Project description:Coupling electron microscopy techniques with in situ heating ability allows us to study phase transformations on the single-nanoparticle level. We exploit this setup to study disorder-to-order transformation of Pt-Fe alloy nanoparticles, a material that is of great interest to fuel-cell electrocatalysis and ultrahigh density information storage. In contrast to earlier reports, we show that Fe (instead of Pt) segregates towards the particle surface during annealing and forms a Fe-rich FeO x outer shell over the alloy core. By combining both ex situ and in situ approaches to probe the interplay between ordering and surface-segregation phenomena, we illustrate that the surface segregation of Fe precedes the ordering process and affects the ordered phase evolution dramatically. We show that the ordering initiates preferably at the pre-existent Fe-rich shell than the particle core. While the material-specific findings from this study open interesting perspectives towards a controlled phase evolution of Pt-Fe nanoalloys, the characterization methodologies described are general and should prove useful to probing a wide-range of nanomaterials.
Project description:A series of nanocrystalline calcium hydroxyapatites was prepared by dry milling and characterized using proton and 31P MAS NMR, TEM, and TGA methods. The samples contained stubby rod-shaped crystals, which length and width varied in the 130-30 and 95-20 nm ranges, respectively. It was confirmed that concentration of structural hydroxyl groups in nanocrystalline apatites decreases with the decreasing crystal size. In the series of the studied apatites, the decrease was from 86 to ca. 50 % in reference to stoichiometric apatite. Water was found in the surface hydrated layer and in the c-axis channels, in which compartments existed as adsorbed and structural, respectively. Molecules of the adsorbed water were capable of moving from the crystal surface into the lattice c-axis channels of apatite. This process introduced considerable structural disorder within and around those channels and reduced the content of the structural hydroxyl groups, particularly in the region underneath the apatite crystal surface.
Project description:Nanocrystalline calcium carbonate (CaCO3) and amorphous CaCO3 (ACC) are materials of increasing technological interest. Nowadays, they are mainly synthetically produced by wet reactions using CaCO3 reagents in the presence of stabilizers. However, it has recently been discovered that ACC can be produced by ball milling calcite. Calcite and/or aragonite are the mineral phases of mollusk shells, which are formed from ACC precursors. Here, we investigated the possibility to convert, on a potentially industrial scale, the biogenic CaCO3 (bCC) from waste mollusk seashells into nanocrystalline CaCO3 and ACC. Waste seashells from the aquaculture species, namely oysters (Crassostrea gigas, low-Mg calcite), scallops (Pecten jacobaeus, medium-Mg calcite), and clams (Chamelea gallina, aragonite) were used. The ball milling process was carried out by using different dispersing solvents and potential ACC stabilizers. Structural, morphological, and spectroscopic characterization techniques were used. The results showed that the mechanochemical process produced a reduction of the crystalline domain sizes and formation of ACC domains, which coexisted in microsized aggregates. Interestingly, bCC behaved differently from the geogenic CaCO3 (gCC), and upon long milling times (24 h), the ACC reconverted into crystalline phases. The aging in diverse environments of mechanochemically treated bCC produced a mixture of calcite and aragonite in a species-specific mass ratio, while the ACC from gCC converted only into calcite. In conclusion, this research showed that bCC can produce nanocrystalline CaCO3 and ACC composites or mixtures having species-specific features. These materials can enlarge the already wide fields of applications of CaCO3, which span from medical to material science.
Project description:A cross-correlative precession electron diffraction - atom probe tomography investigation of Cr segregation in a Fe(Cr) nanocrystalline alloy was undertaken. Solute segregation was found to be dependent on grain boundary type. The results of which were compared to a hybrid Molecular Dynamics and Monte Carlo simulation that predicted the segregation for special character, low angle, and high angle grain boundaries, as well as the angle of inclination of the grain boundary. It was found that the highest segregation concentration was for the high angle grain boundaries and is explained in terms of clustering driven by the onset of phase separation. For special character boundaries, the highest Gibbsain interfacial excess was predicted at the incoherent ∑3 followed by ∑9 and ∑11 boundaries with negligible segregation to the twin and ∑5 boundaries. In addition, the low angle grain boundaries predicted negligible segregation. All of these trends matched well with the experiment. This solute-boundary segregation dependency for the special character grain boundaries is explained in terms of excess volume and the energetic distribution of the solute in the boundary.
Project description:Nanocrystalline/amorphous powder was produced by ball milling of Ti50Cu25Ni20Sn? (at.%) master alloy. Both laser diffraction particle size analyzer and scanning electron microscope (SEM) were used to monitor the changes in the particle size as well as in the shape of particles as a function of milling time. During ball milling, the average particle size decreased with milling time from >320 µm to ~38 µm after 180 min of milling. The deformation-induced hardening and phase transformation caused the hardness value to increase from 506 to 779 HV. X-ray diffraction (XRD) analysis was used to observe the changes in the phases/amorphous content as a function of milling time. The amount of amorphous fraction increased continuously until 120 min milling (36 wt % amorphous content). The interval of crystallite size was between 1 and 10 nm after 180 min of milling with 25 wt % amorphous fractions. Cubic Cu(Ni,Cu)Ti? structure was transformed into the orthorhombic structure owing to the shear/stress, dislocations, and Cu substitution during the milling process.
Project description:The Sm protein Hfq binds small non-coding RNA (sRNAs) in bacteria and facilitates their base pairing with mRNA targets. Molecular beacons and a 16 nt RNA derived from the Hfq binding site in DsrA sRNA were used to investigate how Hfq accelerates base pairing between complementary strands of RNA. Stopped-flow fluorescence experiments showed that annealing became faster with Hfq concentration but was impaired by mutations in RNA binding sites on either face of the Hfq ring or by competition with excess RNA substrate. A fast bimolecular Hfq binding step (∼10(8) M(-1)s(-1)) observed with Cy3-Hfq was followed by a slow transition (0.5 s(-1)) to a stable Hfq-RNA complex that exchanges RNA ligands more slowly. Release of Hfq upon addition of complementary RNA was faster than duplex formation, suggesting that the nucleic acid strands dissociate from Hfq before base pairing is complete. A working model is presented in which rapid co-binding and release of two RNA strands from the Hfq ternary complex accelerates helix initiation 10 000 times above the Hfq-independent rate. Thus, Hfq acts to overcome barriers to helix initiation, but the net reaction flux depends on how tightly Hfq binds the reactants and products and the potential for unproductive binding interactions.
Project description:In this study, the mechanism of stabilizing polyacrylonitrile (PAN) fibers in a short period of time is investigated through probing the effects of oxygen on the structural evolution of PAN under different temperature regimes. It has been found that oxygen has a significant influence on both the chemical and physical structural evolution of PAN fibers, even in a short period of stabilization time, and the influences are dissimilar at different stabilization temperatures. At lower temperatures (below 140 °C), there is no noticeable change in the chemical and physical structures of the PAN fibers. In the mid-temperature range (140-200 °C), oxygen can slightly induce the cross-linking of PAN chains and result in a higher rate of decreasing crystallinity. When the main chemical reactions are initiated at higher temperatures (200-260 °C), oxygen is directly involved in the oxidation reaction of the PAN chains and facilitates cyclization and dehydrogenation. These reactions initiate in the amorphous regions of PAN fibers, and extend to the crystalline regions at elevated temperatures.
Project description:Claims are often found in the literature that metallic materials can be nanocrystallized by severe plastic deformation (SPD). However, SPD does not generate a well-defined nanocrystalline (NC) material, which can be achieved by subsequent annealing/recovery treatment. In this study, molecular dynamics (MD) simulation is employed to study the effect of annealing on structure and mechanical properties of cyclic deformed NC α-iron, which simulates SPD-processed α-iron. It is demonstrated that grain boundaries in the deformed NC α-iron evolve to a more equilibrium state during annealing, eliminating or minimizing the residual stress. The annealing treatment increases the system's strength by reducing dislocation emission sources, and improves material ductility through strengthening grain boundaries' resistance to intergranular cracks. The results indicate that the annealing treatment is an essential process for obtaining a well-defined NC structure with superior mechanical properties.