Synthesis and microstructure of bulk nanocrystalline copper

The synthesis of bulk nanocrystalline copper (NC-Cu) by powder metallurgy is presented, from compaction of nanocrystalline powders to sintering and differential extrusion. At each step of the process, the microstructure is characterized using X-ray diffraction (XRD) analysis, field-emission gun scanning electron microscopy (FEG-SEM), and transmission electron microscopy (TEM). Particular attention is given to the concept of grain size in nanostructured materials and the comparison of results from the different characterization techniques. The fully dense material has a grain size of 100 nm with a microstructure best described in terms of the distribution of high-angle grain boundaries (GBs), twin boundaries, and low-angle GBs. Dislocations occur in half the grains and at most of the twin boundaries. The GBs are shown to be crystalline, and no evidence is found for amorphous interfacial regions. It is proposed that the grain size be defined only in terms of high-angle GBs, excluding low-angle GBs, for the discussion of mechanical properties. In this respect, the microstructure is compared with the NC-Cu material produced by other synthesis techniques. Powder metallurgy (P/M) processing is revealed as an alternative for the production of large-size submicrocrystalline and NC materials.     

Characterization of nanostructured materials using SEM and HREM techniques

A microstructural characterization based on analytical scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HREM) was carried out on nanostructured M50-type steel and also on nanometer-sized gold particles. Both nanostructured materials were prepared with different chemical methods recently reported in the literature. The obtained nanostructured steel powders were subsequently consolidated into bulk samples. The SEM studies of the M50 compound probes show the presence of pores of different sizes. The composition of the specimens indicates small differences with the M50-type steel alloy, with strong variations of the vanadium amount in the cavities of the compound. The HREM images show the presence of small precipitates in the range of a few nanometers in size. The structural characteristics of the grain boundaries between the nanometric crystallites were also explored. The geometrical relationships between adjacent alpha-Fe grains were obtained for some particular boundary arrangements. The nanometric gold particles show diameters which vary from 4 to 11 nm. Some of these particles display twin boundary arrangements. The nature of these twin arrangements was also explored. Theoretical simulations based on the multislice theory of the electron diffraction dynamical theory were carried out mainly to explore the nature of the twin boundaries obtained in the gold particles. Comparisons between the simulated images and the experimental results are presented.     

Effect of prior creep at 1365 K on the room temperature tensile properties of several oxide dispersion strengthened alloys

A study was undertaken to determine if oxide dispersion strengthened (ODS) Ni-base alloys in wrought bar form are subject to a loss of room temperature tensile properties after elevated temperature creep similar to that found in a thin gage ODS alloy sheet. The bar products evaluated included ODS-Ni, ODS-NiCr, and advanced ODS-NiCrAl types. Tensile type test specimens were creep exposed in air at various stress levels at 1365 K and then tensile tested at room temperature. Low residual tensile properties, change in fracture mode, the appearance of dispersoid free bands, grain boundary cavitation, and/or internal oxidation in the microstructure were interpreted as creep degradation effects. This work has shown that many ODS alloys are subject to creep damage. Degradation of tensile properties occurs after very small amounts (≲0.2 pct) of creep strain; ductility being the most sensitive property. The amount of degradation is dependent on the creep strain and is essentially independent of the alloy system. All the ODS alloys which were creep damaged possessed a large grain size (>100 μm). Creep damage appears to be due to diffusional creep which produces dispersoid free bands around boundaries acting as vacancy sources. Low angle and, possibly, twin boundaries were found to act as vacancy sources. The residual tensile properties of two alloys were not affected by prior creep parallel to the extrusion axis. One of these alloys, DS-NiCr(S), was single crystalline. The other alloy, TD-Ni, possessed a small, elongated grain structure which minimized the thickness of the dispersoid free bands produced by diffusional creep.     

Mitigating intergranular attack and growth in lead-acid battery electrodes for extended cycle and operating life

Deterioration in the performance of lead acid batteries is primarily governed by weight loss and growth of the positive electrodes, arising from creep and intergranular corrosion/cracking. The present investigation examines the impact of increasing the frequency of grain boundaries having low-Σ misorientations (Σ≤29), described by the Coincident Site Lattice (CSL) model, which are known to be resistant to these intergranular degradation phenomena. Electrode microstructures of various PbCaSn alloys processed to contain frequencies of special boundaries (in excess of 50 pct) exhibited reductions in weight loss of between 26 and 46 pct accompanied by declines in grid growth of between 41 and 72 pct. Moreover, the distribution of intergranular attack/cracking in the microstructure of these alloys can be predicted on the basis of the frequency of low-Σ special boundaries and grain size. In general, improvements in corrosion and creep/cracking occur without compromising tensile properties such as yield strength, ultimate tensile strength (UTS), and ductility. Modifying the crystallographic structure of grain boundaries in Pb alloy battery electrodes, thus, provides an opportunity for minimizing grid thicknesses (weight) and, hence, material costs in battery production, or for maximizing energy densities (Wh/kg) and cycle life performance.     

Electrochemical formation process and phase control of Mg-Li-Ce alloys in molten chlorides

An electrochemical approach for the preparation of Mg-Li-Ce alloys by co-reduction of Mg,Li and Ce on a molybdenum electrode in KCl-LiCl-MgCl2-CeCl3 melts at 873 K was investigated.Cyclic voltammograms (CVs) and square wave voltammograms indicated that the underpotential deposition (UPD) of cerium on pre-deposited magnesium led to the formation of Mg-Ce alloys at electrode potentials around-1.87 V.The order of electrode reactions was as follows:discharge of Mg(Ⅱ) to Mg-metal,UPD of Ce on the surface of pre-deposited Mg with formation of Mg-Ce alloys,discharge of Ce(Ⅲ) to Ce-metal and after that the discharge of Li+ with the deposition of Mg-Li-Ce alloys,which was investigated by CVs,chronoamperometry,chronopotentiometry and open circuit chronopotentiometry.X-ray diffraction (XRD) illuminated that Mg-Li-Ce alloys with different phases were obtained via galvanostatic electrolysis by different current densities.The microstructures of Mg-Li-Ce alloys were characterized by optical microscopy (OM) and scanning electron microscopy (SEM),respectively.The analysis of energy dispersive spectrometry (EDS) showed that Ce existed at grain boundaries to restrain the grain growth.The compositions and the average grain sizes of Mg-Li-Ce alloys could be obtained controllably corresponding with the phase structures of the XRD patterns.     

Control of annealing twins in type 316 austenitic stainless steel

The twinning frequency expressed as the number of coherent twin boundaries per grain has been investigated as a function of grain size in type 316 and 316L commercial austenitic stainless steels with different carbon contents as well as doped with 30ppm of boron, and subjected to various thermomechanical treatments. Experiments have established that the number of coherent twin boundaries per grain (TB/grain) for grain sizes larger than 0.1 mm, increases linearly with grain size according to the equation: TB/grain = A + K_td, where A and K_t are constants and d is the true volume grain diameter. In the ultrafine and fine grain size range from 1.5 to 100 μm the number of twins per grain is the lowest one and virtually independent of grain size. Both the increase in carbon content by 0.01% and doping with 30 ppm of boron, significantly suppress the formation of twins. Also, the rate of twins formation depends on whether twins are formed during pure grain growth or simultaneous recrystallization and grain growth. The results obtained are explained in terms of the classical Fullman-Fisher theory of twins formation.     

Effect of initial grain size of austenite on hot-deformed structure of Ni-30Fe alloy

The microstructural evolutions of Ni-30Fe alloys during hot deformation are investigated. Hot-deformed structures of Ni-30Fe alloys with initial austenite grain sizes of 20 and 140 μm are examined under various compressive strains and deformation temperatures. As the initial austenite grain size decreases, dynamic recrystallization (DRX) occurs at lower compressive strain and lower deformation temperature. At deformation temperatures where dynamic recovery occurs instead of the DRX, hot-deformed structures consist of recovered elongated grains until fine-equiaxed grains are evolved by geometric DRX. Critical compressive strain for the geometric DRX decreases with the decrease of initial austenite grain size. Geometric DRX is evolved by the impingement of serrated grain boundaries. The decrease of initial grain size is considered to reduce the critical compressive strain needed for the impingement of serrated grain boundaries. The changes in the effective thickness of austenite grain according to the compressive deformation are examined and the effects of the restoration processes on the effective thickness of austenite grain are discussed.     

Regularities of Formation and Degradation of the Microstructure and Properties of New Ultrafine-Grained Low-Modulus Ti–Nb–Mo–Zr Alloys

Abstract—Regularities of the formation of ultrafine-grained (UFG) and submicrocrystalline (SMC) structures in new nickel-free low-modulus Ti–Nb–Mo–Zr titanium β alloys under the action of plastic deformation have been studied. Temperature–time ranges of the development of dynamic recrystallization processes under the simultaneous action of temperature and plastic deformation are determined. A type-II recrystallization diagram of the Ti–28Nb–8Mo–12Zr alloy is constructed and analyzed. It is shown using scanning electron microscopy and the electron backscatter diffraction method that the UFG structure with an average grain size of no more than 7 μm and high fraction of high-angle grain boundaries is formed in the investigated alloys as a result of longitudinal rolling, followed by annealing for quenching. It is found that the formation of the UFG structure leads to a significant increase in the strength and plastic characteristics of these alloys. The regularities of the formation of UFG and SMC structures in titanium β alloys Ti–28Nb–8Mo–12Zr and industrial VT30 under the action of plastic deformation by the helical rolling method are studied. It is shown that the helical rolling of the VT30 alloy leads to the formation of the homogeneous UFG state as opposed to the Ti–28Nb–8Mo–12Zr alloy, where this method causes structure softening with micropores and microcracks formed in the central region. It is possible to form a nanostructured state with an average grain size of about 100 nm in Ti–Nb–Mo–Zr titanium β alloys using the high-pressure torsion method.     

Deformation behavior of bimodal nanostructured 5083 Al alloys

Cryomilled 5083 Al alloys blended with volume fractions of 15, 30, and 50 pct unmilled 5083 Al were produced by consolidation of a mixture of cryomilled 5083 Al and unmilled 5083 Al powders. A bimodal grain size was achieved in the as-extruded alloys in which nanostructured regions had a grain size of 200 nm and coarse-grained regions had a grain size of 1 μm. Compression loading in the longitudinal direction resulted in elastic-perfectly plastic deformation behavior. An enhanced tensile elongation associated with the occurrence of a Lüders band was observed in the bimodal alloys. As the volume fraction of coarse grains was increased, tensile ductility increased and strength decreased. Enhanced tensile ductility was attributed to the occurrence of crack bridging as well as delamination between nanostructured and coarse-grained regions during plastic deformation.     

Nucleation of grain boundary cavities under the combined influence of helium and applied stress

Modelling cavity nucleation at grain boundaries in structural alloys under the combined influence of helium and stress is the primary objective of this paper. The role of stress in cavity nucleation is analyzed using an extension of classical theory by taking into account grain boundary sliding to describe stress concentration buildup and relaxation at particles and triple-point junctions. Helium clustering in the matrix is modeled using rate theory. The helium flux to grain boundaries is determined by the application of sink strength theory which takes into account the various competing clustering mechanisms in the matrix. Helium clustering on grain boundaries is also theoretically investigated using rate theory. The work agrees with experimental observations showing that irradiation results in grain boundary bubble densities which are orders of magnitude larger than cavity populations observed in conventional creep experiments. It is shown that even if the total injected helium is as little as one part per million, it can result in grain boundary bubble densities on the order of 10¹³ m⁻². Such cavity population exceeds typical grain boundary cavity densities associated with creep experiments. Grain boundary bubble densities are shown to reach steady state for injected helium amounts on the order of 10 parts per million.     

Austenite steels strengthened by means of nano-scale twins

Recent investigations indicated that metals can be effectively strengthened by numerous twin boundaries (TBs) with twin/matrix lamellar thicknesses in the nanometer regime.Superior strength-ductility synergies have been achieved with the nano-twin strengthening mechanism.In this talk,the novel nano-twin strengthening will be applied to austenite steels including 316L stainless steel and a Fe-Mn steel in order to optimize their strength-ductility combinations.The steels are processed by means of dynamic plastic deformation(DPD,i.e.,plastic deformation at high strain rates).Single-phased(austenite) bulk nanostructured steel specimens were prepared,consisting of nano-sized grains embedded with nano-scale twin bundles.The as-prepared nanostructured samples were annealed at various conditions,resulting in partial recrystallization of the nanostructures and forming a mixture structure of coarse-grains embedded with nano-twin bundles.Strength and ductility of the austenite steels with different amount of nano-twin bundles are analyzed.Measurements showed the nano-twin strengthen austenite steels can be superstrong (with yield strength above 1 GPa) together with a considerable ductility(elongation-to-failure >20%).     

Understanding the Effect of Grain Boundary Character on Dynamic Recrystallization in Stainless Steel 316L

Dynamic recrystallization (DRX) occurs during high-temperature deformation in metals and alloys with low to medium stacking fault energies. Previous simulations and experimental research have shown the effect of temperature and grain size on DRX behavior, but not the effect of the grain boundary character distribution. To investigate the effects of the distribution of grain boundary types, experimental testing was performed on stainless steel 316L specimens with different initial special boundary fractions (SBF). This work was completed in conjunction with computer simulations that used a modified Monte Carlo method which allowed for the addition of anisotropic grain boundary energies using orientation data from electron backscatter diffraction (EBSD). The correlation of the experimental and simulation work allows for a better understanding of how the input parameters in the simulations correspond to what occurs experimentally. Results from both simulations and experiments showed that a higher fraction of so-called “special” boundaries (e.g., Σ3 twin boundaries) delayed the onset of recrystallization to larger strains and that it is energetically favorable for nuclei to form on triple junctions without these so-called “special” boundaries.     

Diffusion of Zn in Nanostructured Aluminum Alloys Produced by Surface Mechanical Attrition Treatment

After surface nanocrystallization of pure Al and a cast Al-Si alloy through surface mechanical attrition treatment (SMAT), 200- to 300-??m-thick Zn coatings were deposited on the nanostructured surface using the clod spray technique. Subsequently, diffusion of Zn into the Al substrate was induced by postspray annealing treatment at various temperatures for different times. The diffusion kinetics of Zn in the nanostructured surface layers was studied in terms of the Zn concentration profile in the substrate by using scanning electron microscopy (SEM) and electron probe microscopy analysis (EPMA). Experimental results show that not only the diffusivity of Zn in the nanocrystalline grains is significantly increased compared with the diffusion in the coarse grained counterpart, but the temperature at which noticeable Zn diffusion in Al alloys occurs is also reduced from 573?K (300?°C) in coarse-grained Al alloys to 523?K (250?°C) in nanostructured alloys. In addition, because the nanocrystalline grains produced by SMAT in Al-Si alloys are much smaller than those in pure Al due to the effect of eutectic Si, the diffusion of Zn in the SMATed Al-Si alloy is much faster than that in the SMATed pure Al. It is believed that the high diffusivity of Zn in the nanocrystalline Al grains is attributed to the large fraction of grain boundaries that act as fast diffusion channel. The effect of thermal stability of the nanocrystalline grains on Zn diffusion in the SMATed Al alloys is also discussed.     

Computer simulation of recrystallization—III. Influence of a dispersion of fine particles

Two-dimensional Monte Carlo simulations of recrystallization have been carried out in the presence of incoherent and immobile particles for a range of different particle fractions, a range of stored energies and a range of densities of potential nuclei (embryos). For stored energies greater than a critical value (H/J > 1) the recrystallization front can readily pass the particles leading to a random density of particles on the front and a negligible influence of particles on the recrystallization kinetics. At lower stored energies the particles pin the recrystallization front leading to incomplete recrystallization. However at very low particle fractions, when the new grain has grown much larger than the matrix grains, before meeting any particles, the new grains can complete the consumption of the deformed grains giving complete “recrystallization” by a process that appears to be similar to abnormal grain growth. Particles are, as reported previously, very effective at pinning grain boundaries, both of the deformed and recrystallized grains, when boundaries migrate under essentially the driving force of boundary energy alone. Such boundaries show a density of particles that rises rapidly from the random value found at the start of the simulation. As a consequence, particles very strongly inhibit normal grain growth after recrystallization. Such growth can only occur if the as-recrystallized grain size is less than the limiting grain size seen in the absence of recrystallization. Under these circumstances a small increment of grain growth occurs until the grain boundaries once again acquire a higher than random density of particles.     

Effect of Dislocation Mechanisms during Extrusion of Nanostructured Aluminum Powder Alloy

Nanostructured Al-3.0Fe-0.42Cu-0.37Mn powder alloy was deformed by extrusion over a temperature range of 375 °C to 425 °C, a ram speed range of 1 to 30 mm/s, and an extrusion rate of 10:1. Flow stresses and strain rates were calculated from the experimental ram pressures and speeds. The stress–strain-rate–temperature relationship in the extrusion of the nanostructured alloy was found to be similar to that in hot-worked conventional materials. The extrusion, torsion, compression, and creep data of nanostructured and conventional materials, extending over ten orders of magnitude of strain rate and over two orders of magnitude of stress, were correlated by a hyperbolic-sine constitutive equation, because the power and exponential laws lose linearity at high and low stresses, respectively. The hyperbolic-sine equation is widely used to correlate the hot-working behavior of conventional materials. It was concluded that the hot working of nanostructured powders is a thermally activated process in which the rate-controlling mechanism is the climb of edge dislocations. Microstructural changes in the consolidated alloys as a function of the extrusion conditions were investigated. An analysis was made of the dislocation behavior in very small grains of nanostructured metal by transmission electron microscopy (TEM) and we identified a dislocation structure and the different ways it appears in 40- to 100-nm Al-alloy grains. We also discuss the thermally activated propagation of dislocations and their interactions with shear bands/grain boundaries (SBs/GBs), and dislocation loops. Microstructural features including low-angle GBs, high-angle GBs, and equilibrium GBs and subgrain boundaries were observed. Dislocation structures under a deformation condition were studied to investigate the microstructural evolutions, which revealed some unique microstructural features such as dislocation tangle zones (DTZs) and dense-dislocation walls (DDWs), and the recovery process is discussed herein.     

Misoriented dislocation substructures and the fracture of polycrystalline Cu–Al alloys

The evolution of the dislocation substructure in polycrystalline Cu–Al alloys with various grain sizes is studied during deformation to failure. A relation between the fracture of the alloys and the forming misorientation dislocation substructures is revealed. Microcracks in the alloy are found to form along grain boundaries and the boundaries of misoriented dislocation cells and microtwins.     

Role of dynamic precipitation on the strengthening mechanism of cryorolled 6063 Al alloy

6063 Al alloys was cryorolled under solutionized (sample1) and peak aged condition (sample2) to study the role of dynamic precipitation on the strengthening mechanism. It is observed that in case of sample1 dislocations density is more compare to sample2. In the 1^st case high angle sub grains (presence of high fraction of HAGBs) of less than 100 nm in size have been generated during cryorolling. In case of sample2, grains are aligned along the rolling direction. This is obvious that the higher densities of dislocations (in sample1) restrict the grain boundaries to be aligned along the rolling direction. Therefore, the grain boundaries are aligned along the rolling direction only in case of sample2. Whereas such type of alignments of grain boundaries are not observed in case of sample1. Presence of very fine grains along with high density of dislocations are responsible for attaining higher strength of sample1 compare to sample2.     

晶粒细化对Cu-40Ni合金在酸性含Cl-介质中耐蚀性能的影响

采用电弧熔炼（CA）和机械合金化（MA）通过热压烧结工艺制备了晶粒尺寸差别较大的Cu-40Ni合金，借助于PARM273A和M5210电化学综合测量仪，利用动电位扫描法和交流阻抗技术对比研究了上述合金在酸性含Cl^-介质中的腐蚀电化学性能以及腐蚀机制。结果表明：两种合金的腐蚀电位随时间逐渐稳定，在中性Na2SO4溶液中加入H2SO4和NaCl后，两种合金的自腐蚀电位负移；晶粒细化后，两种合金的自腐蚀电位则正移。两种合金在中性及酸性含Cl^-介质中均存在钝化现象，但在酸性含Cl^-介质中钝化区间很短，钝化能力较弱。两种合金的交流阻抗谱均由单容抗弧组成，反应由电化学过程控制。晶粒细化后，合金中存在大量晶界，参与腐蚀反应的活性原子数增加，促使MACu40Ni合金的腐蚀速度高于CACu-40Ni合金。     

Grain boundary segregation of boron in INCONEL 718

The segregation behavior of boron at grain boundaries in two INCONEL 718⁺ based alloys with different B concentrations was studied. The alloys, one containing 11 ppm of B and the other 43 ppm, were homogenized at 1200 °C for 2 hours followed by water quenching and air cooling. A strong segregation of boron at grain boundaries was observed using secondary ion mass spectrometry after the heat treatment in both the alloys. The segregation was found mainly to be of nonequilibrium type. The homogenized samples were also annealed at 1050 °C for various lengths of time. During annealing, boride particles were observed to first form at grain boundaries and then to dissolve on continued annealing at 1050 °C. The mechanisms of segregation and desegregation of B are discussed.     

The influence of prior deformation on hydride precipitation in zircaloy

Precipitation of hydrides has been studied in samples of Zircaloy subjected to prior tensile or compressive deformation before charging with hydrogen. The mean residual stress pattern in the alloys prior to charging was assessed by neutron diffraction techniques and provided a rough guide as to the preferred site of hydride nucleation. Heterogenous hydride nucleation at grain boudaries or twin boundaries was commonly found in samples subjected to 4% prior deformation, while transgranular hydrides were most frequently observed after a prior 1/2% compressive deformation or an annealing. The local stress state at grain boundary facets or twins is thought to be the deciding factor in determining where hydrides nucleate and how hydride stacks form.