Volume 115, Issue 2

This paper reviews the recent progress in understanding the atomic mechanisms of short-circuit diffusion along materials interfaces, such as grain and interphase boundaries, as well as lattice and interfacial dislocations/disconnections. Recent atomistic computer simulations have shown that short-circuit diffusion is dominated by collective atomic rearrangements in the form of strings and rings of mobile atoms. The process is dynamically heterogeneous in space and time and has many features in common with atomic dynamics in supercooled glass-forming liquids. We discuss examples of grain boundary, interphase boundary, and dislocation diffusion in metals and alloys, including the solute effect on the diffusion rates and mechanisms. Interphase boundaries are exemplified by Al–Si interfaces with diverse orientation relationships and atomic structures. The hierarchy of short-circuit diffusion paths in materials is reviewed by comparing the rates of grain boundary, interphase boundary, and dislocation diffusion. Future directions in the field of short-circuit diffusion in defect core regions are discussed.

Grain boundary self- and solute (cobalt) diffusion in tungsten was found [Lee et al., Scr. Metall, 1988; Lee et al., Col. de Physique, 1990] to exhibit discontinuities in the Arrhenius behavior at the homologous temperatures of 0.36 < T / T m < 0.4 that surprisingly match the activation sintering temperature of W ( T m is the melting point). In the present work, this unusual grain boundary diffusion phenomenon is discussed in terms of a fundamental grain boundary phase transition in W. The experimental data are analysed with respect to predicted segregation-induced grain boundary phase transformation. Competing co-segregation of impurity elements (carbon and phosphor) might induce a discontinuous grain boundary segregation and invoke a grain boundary phase transition which modifies the grain boundary mobilities of substitutional atoms. The improved understanding of grain boundary phase transitions is expected to provide a breakthrough in interpreting the exact mechanism of W-activated sintering.

Diffusion of Bi and Ag in a series of polycrystalline Cu–Bi alloys is investigated using a radiotracer technique and applying the 207 Bi and 110 m Ag isotopes, respectively. Together with the previous measurements (Divinski S., Lohmann M., Herzig C., Straumal B., Baretzky B., Gust W. Grain-boundary Melting Phase Transition in the Cu−Bi System. Phys. Rev. B 2005 , 71 , 104104), a temperature–concentration interval of strong, by orders of magnitude, enhancements of Bi grain boundary diffusion rates is distinguished and the results are interpreted in terms of a grain boundary pre-wetting/wetting phase transition. Grain boundary diffusivity of Ag exhibits as well a step-wise increase with rising Bi content, mirroring the behaviour observed for the Bi tracer. However, contrary to the Bi tracer atoms for which grain boundary enhancement is observed at about 60 ppm of Bi in Cu–Bi alloys, this transition is revealed by the Ag tracer atoms at a significantly higher concentration, specifically between 90 and 100 ppm of Bi at 1080 K. The Ag diffusion rates in alloys with a moderate Bi content turn out to be not affected by the Bi-induced grain boundary phase transition and the measured grain boundary diffusion coefficients of Ag are nearly the same as those determined for pure polycrystalline Cu. This spectacular result suggests a strong heterogeneity of Bi segregation and Bi-induced phase transition for general high-angle grain boundaries in a given alloy. The behaviour is discussed in terms of the extrinsic grain boundary defects and their impact on mechano-chemical coupling which is accompanying the grain boundary phase transitions.

We deposited a 30 nm-thick Au film on single crystalline KBr substrate and studied the solid state dewetting behavior of the film at a temperature of 350 °C. At this temperature, the ions of the KBr compound exhibit significant mobility along the Au–KBr interface, which affects the morphology and kinetics of the solid state dewetting. We performed statistical morphology analysis of the Au–KBr interface by selectively dissolving the KBr substrate after the dewetting heat treatments and subsequent atomic force microscopy imaging of the “upside-down” oriented Au film. We demonstrated that atomic mobility at the interface leads to embedding of the partially dewetted Au film into the KBr substrate. We proposed a quantitative model of the shape evolution of a disc-shaped Au particle on the KBr substrate under the condition of finite interface mobility of the substrate species. The model predictions were consistent with the experimentally observed sinking rates of Au nanostructures.

When a multicomponent NdFeB-based magnetic alloy is deformed using high-pressure torsion (HPT), a quasi-stationary state is reached after 2.5 anvil revolutions, which corresponds to an equivalent strain of ∼40 at the sample mid-radius. In this state, torque self-oscillations are observed with a period of about 1.5 s and an amplitude of ∼10 % around the average value of 550 N m −1 . Such self-oscillations are accompanied by strong acoustic emission. Before HPT, the alloy under study has an almost rectangular hysteresis loop with saturation magnetization J s = 135 emu g −1 and coercivity H c = 34.8 kOe. HPT deformation at initial stages transforms this alloy to the class of soft magnets: H c drops to 1.35 × 10 −4  kOe, while J s practically does not change. An increase in strain leads to a gradual increase in H c to 9.61 kOe and a decrease in J s to ∼100 emu g −1 at the number of anvil revolutions n = 7. This is explained by HPT modification of the regular grain-boundary network of neodymium-rich paramagnetic phase layers. These layers provide magnetic isolation between grains of the Nd 2 Fe 14 B ferromagnetic phase. Periodic changes in torque and J s with increasing torsion angle are caused by transitions from the amorphous phase to the crystalline one and vice versa.

In this paper the effect of diffusion formation of supersaturated solid solution in the Al–Ge system is discussed. It was shown that at relatively low temperatures of diffusion annealing, Ge concentration in Al-based solid solution became higher than the solubility limit at given temperatures. The maximal concentration of Ge was determined by extrapolation of the diffusion profile on the Ge/Al interface. Analysis of diffusivity of Al in Ge allowed to suggest that slow diffusion in Ge restricts the formation of Ge-based solid solution. Qualitative approach confirmed this suggestion.