Modeling of the γ → α transformation in steels

A mathematical physically based model of the decomposition of undercooled austenite (γ-phase) with the formation of ferrite (α-phase) and pearlite has been developed. The model differs from the currently existing analogs by a new approach to the inclusion of the effect of complex alloying of steels on the nucleation rate of ferrite grains and on the mobility of the α/γ-phase boundary. In the model, the effect of alloying of steels with substitutional elements on the diffusion coefficient of carbon in the bulk of austenite is taken into account. The results of the modeling of the kinetics of austenite decomposition and the calculation of the final ferrite grain size are in good quantitative agreement with the experimental data obtained for a set of steels with a wide range of chemical compositions.     

Grain boundary impurity segregation and neutron irradiation effects in ferritic alloys

Segregation of alloying and impurity elements to grain boundaries in ferritic steels and alloys is known to modify the mechanical properties. This paper considers segregation of such elements, in particular phosphorus and carbon, that occur in ferritic nuclear pressure vessel steels subject to neutron irradiation and temperature typical of that encountered in service. Models are presented that allow the prediction of equilibrium and non-equilibrium segregation of phosphorus to grain boundaries and also take into account synergistic interaction with carbon under various combinations of neutron-irradiation temperature. These are related to a wide range of experimental observations compiled from data in the literature for mainly phosphorus and carbon measured at grain boundaries in neutron-irradiated ferritic vessel steels and alloys. The predictions from the segregation models are compared with these experimental data. The discussion provides a rationalization for the apparent variability in the measured grain boundary phosphorus compositions and thereby fracture susceptibility for various nuclear pressure vessel ferritic steels.     

Diffusion kinetics of gaseous fission products arising under uranium fuel irradiation

A physical mechanism underlying the diffusion migration of gaseous fission products near the triple joints of grain boundaries during nuclear fuel burnout is suggested and mathematically substantiated. The diffusion kinetics is analyzed with regard to the first invariant of the stress tensor for a given structural defect. The results of mathematical simulation are of interest for analysis of nuclear fuel swelling due to the growth of intergranular pores and formation of channels for fission product migration along the grain boundaries.     

Scientific basis for cold brittleness of structural BCC steels and their structural degradation at below zero temperatures

The paper considers the physics of cold brittleness of structural bcc steels and methods of reducing the ductile-brittle fracture temperature. A complex study was performed to examine the degradation of structural phase state of pipe steel 09Mn2Si from the main gas pipeline of Yakutia after long-term (over 3 0 years) operation. Important regularities of degradation of pearlite colonies with carbide precipitation on ferrite grain boundaries were revealed. This phenomenon is associated with brittle fracture of gas pipelines. It is shown that the low-temperature kinetic processes in main pipelines which define the degradation of their structure and properties are related to interstitial athermal structural states in the zones of local crystal structure curvature. This is a fundamentally new, as yet unknown, mechanism. Pipe steels in warm rolling acquire a longitudinal textured band structure with alternating bands of initial ferrite grains and bands of fine grains with carbide precipitates formed during lamellar pearlite degradation. This type of structure allows for a shift of ductile-brittle transition temperature down to -80°C and ductility δ = 22% at this temperature. The production of high-curvature vortex structure in pipe steel surface layers results in a 3.5-fold increase in their service life.     

Grain boundary curvature and grain growth kinetics with particle pinning

Second-phase particles are used extensively in design of polycrystalline materials to control the grain size. According to Zener’s theory, a distribution of particles creates a pinning pressure on a moving grain boundary. As a result, a limiting grain size is observed, but the effect of pinning on the detail of grain growth kinetics is less known. The influence of the particles on the microstructure occurs in multiple length scales, established by particle radius and the grain size. In this article, we use a meso-scale phase-field model that simulates grain growth in the presence of a uniform pinning pressure. The curvature of the grain boundary network is measured to determine the driving pressure of grain growth in 2D and 3D systems. It was observed that the grain growth continues, even under conditions where the average driving pressure is smaller than the pinning pressure. The limiting grain size is reached when the maximum of driving pressure distribution in the structure is equal to the pinning pressure. This results in a limiting grain size, larger than the one predicted by conventional models, and further analysis shows consistency with experimental observations. A physical model is proposed for the kinetics of grain growth using parameters based on the curvature analysis of the grain boundaries. This model can describe the simulated grain growth kinetics.     

A detailed model for the flame synthesis of carbon nanotubes and nanofibers

Many experimental investigations of CNT/CNF flame synthesis have been recently reported. However, there are as yet no comprehensive models regarding their formation, growth or structure. Herein, a CNT/CNF growth rate model is proposed that is applicable for any method of CNT/CNF production (although our particular interest lies in flame synthesis in ethylene/air flames). While it is usual for most existing models to consider only a single carbon-carrying gas that contributes towards carbon deposition, our extended model can consider a complex hydrocarbon mixture that can mimic a flame environment. The model shows that before carbon nucleation is initiated, the surface density of carbon atoms increases as they are added through diffusion from the leading face of the catalyst nanoparticle. Over time, the diffusion potential decreases due to a reduction in the carbon atom concentration gradient. However, with the onset of nucleation and growth, diffusion is reinstated as the major driving potential for carbon atom transport through the nanoparticle. Steady carbon deposition and filament growth occurs once there is a stable carbon cluster size due to nucleation. The results support our hypothesis that flame synthesis can be a much faster and higher throughput process than CVD. The CNT/CNF growth rate decreases with increasing height above the burner. Decreasing temperature at higher locations leads to slower catalyst deactivation, but the CO concentration, which is the major contributor to carbon deposition, also decreases with increasing height above the burner. One of the major findings in this work is the contribution of CO to CNT formation by flame synthesis. The concentration of hydrocarbons in the vicinity of the toroidal zone near, which most of the CNT growth is observed, is negligible compared to CO concentration. Our results provide a basis to conduct future multiscale simulations of CNT/CNF growth.     

高He通量注入条件下F/M和ODS钢中纳米微结构对He泡形核和长大的影响

利用LEAF装置提供的2 MeV的He离子,在500和600 °C分别对新型F/M钢-SIMP钢和ODS钢(MA956和Eurofer-ODS钢)注入1×1017 ions/cm2的高通量He离子,借助透射电子显微镜,表征了辐照后三种材料的肿胀行为,验证了各材料中纳米微结构(晶界,析出相和纳米氧化物)对辐照后He泡成核和长大的影响。结果表明,基于材料中晶界和析出相对He泡生长的抑制作用,温度为500 °C时,SIMP和Eurofer-ODS钢表现出较高的抗辐照肿胀性能,而MA956中纳米界面He泡成核和长大作用不明显,表现出较差的抗辐照肿胀性能;此外,温度为600 °C时,Eurofer-ODS钢由于其晶界和氧化物界面的较强作用,表现出较好的抗辐照肿胀性能。总体来说,在高He通量注入条件下,材料中纳米结构的存在会抑制He泡长大的过程,但不同材料中纳米结构对He影响作用不同。     

Grain boundary interdiffusion in the case of concentration-dependent grain boundary diffusion coefficient

The grain boundary diffusion in a binary system which exhibits a grain boundary phase transition is considered in the framework of Fisher's model. The kinetic law of the growth of the grain boundary phase and the distribution of the diffusant near the grain boundary are calculated. The method of determining of the concentration dependence of the grain boundary diffusion coefficient from the experimentally measured penetration profiles of the diffusant along the grain boundaries is suggested. The experimental results on Zn diffusion in Fe(Si) bicrystals, Ni diffusion in Cu bicrystals and grain boundary grooving in Al in the presence of liquid In are discussed in light of the suggested model.     

Stabilization of growth of a pearlite colony because of interaction between carbon and lattice dilatations

The previously proposed model of pearlite transformation develops taking into account the possible interaction between carbon and lattice dilatations arising in austenite near the pearlite colony. The normal stresses caused by the colony stimulate autocatalysis of plates, and tangential stresses promote the stabilization of the transformation front. The mechanism of ferrite branching, which can play an important role in the kinetics of pearlite and bainite transformations, is discussed.     

Diffusion and segregation along grain boundary at the electrolyte-anode interface in IT-SOFC

The atomic level chemical and microstructural features of grain boundaries in gadolinium-doped ceria (GDC) electrolyte thin film supported by Ni-GDC cermet anode were characterized by high resolution transmission electron microscope (HR-TEM) and scanning TEM (STEM). It was found that metallic Ni can diffuse from the anode into the thin film electrolyte along grain boundaries. In addition, Ce and Gd can also diffuse and segregate at grain boundaries between Ni grains in the anode substrate. HR-TEM observations revealed that Ni diffusion and segregation at grain boundaries between GDC grains enhanced the inhomogeneity and led to microstructural changes at grain boundary regions, i.e. the formation of superstructure. The observations also indicated that enhanced inhomogeneity at grain boundaries might play a significant role in the conductivity of GDC electrolyte film in solid oxide fuel cells.     

Microstructure evolution of T91 steel after heavy ion irradiation at 550 ℃

Fe-Cr ferritic/martensitic (F/M) steels have been proposed as one of the candidate materials for the Generation IV nuclear technologies. In this study, a widely-used ferritic/martensitic steel, T91 steel, was irradiated by 196-MeV Kr⁺ ions at 550 ℃. To reveal the irradiation mechanism, the microstructure evolution of irradiated T91 steel was studied in details by transmission electron microscope (TEM). With increasing dose, the defects gradually changed from black dots to dislocation loops, and further to form dislocation walls near grain boundaries due to the production of a large number of dislocations. When many dislocation loops of primary a₀/2<111> type with high migration interacted with other defects or carbon atoms, it led to the production of dislocation segments and other dislocation loops of a₀<100> type. Lots of defects accumulated near grain boundaries in the irradiated area, especially in the high-dose area. The grain boundaries of martensite laths acted as important sinks of irradiation defects in T91. Elevated temperature facilitated the migration of defects, leading to the accumulation of defects near the grain boundaries of martensite laths.     

Investigation of solid-state reaction in Ag/Sn nanostructured thin films at room temperature

Diffusion intermixing processes in nanostructured Ag/Sn thin-film system at room temperature were investigated by means of secondary neutral mass Spectrometry depth profiling technique. As it was confirmed by X-ray diffraction too, the reaction started already in the as-deposited sample. Since the bulk diffusion was frozen at room temperature, the Ag₃Sn phase was formed along the grain boundaries (GBs), gradually consuming the interior of grains, and was grown perpendicular to the GBs. At the same time, formation and growth of a small compact reaction layer near the interface were observed and the shift of the bordering parallel interfaces was controlled by GB diffusion. From the kinetics of the diffusion process in the above two mechanisms, both the interface velocity in the diffusion-induced grain boundary motion regime as well as the coefficient of parabolic growth in the planar growth regime were determined.     

Scanning infrared microscopy investigation of copper precipitation in cast multicrystalline silicon

The behavior of copper precipitation in cast multicrystalline silicon (mc-Si) annealed at different temperatures under air cooling (30 K/s) or slow cooling (0.3 K/s) was investigated by scanning infrared microscopy (SIRM). Comparing to Czochralski-grown silicon (Cz-Si), copper precipitated more easily in mc-Si, and the lowest temperature of copper precipitation in mc-Si was about 700 °C, lower than that in Cz-Si. It was also observed that copper preferably precipitated on grain boundaries so that near the grain boundaries the denuded zone formed. The results indicate that the defects including dislocations, grain boundaries and microdefects, as the heteronucleation sites, enhanced copper precipitation. Moreover, cooling rates had a great influence on the copper precipitation, especially at lower annealing temperatures. Generally air cooling led to the formation of high density of copper-precipitate colonies.     

Modeling of polysilicon diffusion sources during rapid optical annealing

A new model for polysilicon diffusion sources is presented. It considers the following effects: 1) dopant diffusion in grains, in grain boundaries and in the single-crystal silicon substrate, 2) dynamic dopant segregation between grain and grain boundary phases and between the phases of polysilicon and the single-crystal silicon substrate, 3) dynamic dopant activation or clustering in grains and in the single-crystal silicon substrate, 4) dynamic grain growth depending on local grain size and local electron density. These mechanisms with completely different time scales are modeled simultaneously. For the first time this allows the analysis of furnace and rapid optical annealing processes with arbitrary grain growth kinetics even during epitaxial realignment. The advanced model for segregation allows for the effect that dopants in grain boundaries and active dopants in grains as well as in the single-crystal silicon substrate find only a limited number of sites which can be occupied. These limitations are necessary to explain the dopant distributions in polysilicon and in the single-crystal silicon substrate. For the first time the coupling between the concentration of active dopants in grains, between the concentration of dopants in grain boundaries and between the local grain size is shown during doping enhanced grain growth.     

Helium trapping at dislocations,precipitates and grain boundaries

Helium bubble formation was observed in austenitic stainless steels by transmission electron microscopy following implantation of 30 to 1000 appm helium at room temperature and annealing at 700 to 800°C. Helium bubble distributions at dislocations and at various grain boundaries and precipitates were studied. It was found that interfacial dislocations play a dominant role in bubble nucleation at grain and interphase boundaries but not at Tic-matrix interfaces. Particularly high trapping of helium was observed at Tic precipitate-matrix interfaces which is attributed to an inhomogeneous ripening mechanism.     

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.     

Kinetics of the eutectoid colony growth in a solid solution for simple alloy models

A simple model, which reflects the main features of the phase equilibria between austenite, ferrite, and cementite, is proposed to study the growth kinetics of pearlite-type eutectoid colonies. The previously developed microscopic theory of diffusional phase transformations in alloys developed earlier is used to simulate steady-state colony growth for several versions of this model. The existing phenomenological approaches are found to describe the main features of the colony growth kinetics qualitatively correctly; however, these approaches are insufficient to draw quantitative conclusions. The changes in the colony front shape as temperature T approaches eutectic point T _e and the structure of the interphase boundaries at various T are studied. At T near T _e , the initial phase (austenite) is found to wet the boundaries between the forming phases (ferrite, cementite), which results in a sharp increase in the interphase boundary thickness and a decrease in the junction angle between the phases at the colony front. The differences in the diffusion mobilities of interstitial (carbon) atoms in different phases are shown to be important to adequately describe the colony growth kinetics.     

Effects of B segregation on Mo-rich phase precipitation in S31254 super-austenitic stainless steels: Experimental and first-principles study

Precipitation in super-austenitic stainless steels will significantly affect their corrosion resistance and hot workability. The effects of Cr and Mo on precipitation behaviors were mainly achieved by affecting the driving force for precipitation, especially Mo has a more substantial promotion effect on the formation of the σ phase than Cr. In the present study, B addition to the S31254 super-austenitic stainless steels shows an excellent ability to inhibit precipitation. The effect of B on the precipitation behaviors was investigated by microstructure characterization and theoretical calculations. The experimental observation shows that the small addition of B inhibits the formation of the σ phase along grain boundaries and changes from continuous to intermittent distribution. Moreover, the inhibitory effect increased obviously with the increase of B content. The influence of B addition was theoretically analyzed from the atomic level, and the calculation results demonstrate that B can inhibit the formation of σ phase precipitates by suppressing Mo migration to grain boundaries. It is found that B and Mo are inclined to segregate at Σ 5 and Σ 9 grain boundaries, with B showing the most severe grain boundary segregation tendency. While B distribution at the grain boundary before precipitation begins, the segregation of Mo and Cr will be restrained. Additionally, B's occupation will induce a high potential barrier, making it difficult for Mo to diffuse towards grain boundaries.     

Grain Boundary Kinetics in Oxide Ceramics with the Cubic Fluorite Crystal Structure and its Derivatives

Kinetics of grain boundaries in oxides with the cubic fluorite structure and its derivatives has been investigated using fine grain ceramics that are fully dense. Grain growth measurements in these materials have provided information on grain boundary diffusivity over a diffusion distance of the order of the initial grain size. With the addition of solute cations, grain boundary mobility can be varied over many orders of magnitude, often with very different activation energies. This is caused by the variation of defect population and the defect-solute association. Definitive evidence for solute drag has also been observed in some cases, but solute drag can not be confirmed as a general mechanism in solid solutions. Lastly, while grain boundary at low temperature may continue to serve as a fast diffusion path, it may not be able to migrate because of additional pinning mechanisms such as those exerted by grain boundary nodal points or lines. This means that sintering without grain growth is possible, opening up an avenue for obtaining ultrafine ceramics by pressureless sintering.     

Modeling of spatiotemporal patterns in bacterial colonies

A diffusion-reaction model for the growth of bacterial colonies is presented. The often observed cooperative behavior developed by bacteria which increases their motility in adverse growth conditions is here introduced as a nonlinear diffusion term. The presence of this mechanism depends on a response which can present hysteresis. By changing only the concentrations of agar and initial nutrient, numerical integration of the proposed model reproduces the different patterns shown by Bacillus subtilis OG-01.