Structural and chemical embrittlement of grain boundaries by impurities: A general theory and first-principles calculations for copper

First-principles calculations of the Sigma 5(310)[001] symmetric tilt grain boundary in Cu with Bi, Na, and Ag substitutional impurities provide evidence that in the phenomenon of Bi embrittlement of Cu grain boundaries electronic effects do not play a major role; on the contrary, the embrittlement is mostly a structural or "size" effect. Na is predicted to be nearly as good an embrittler as Bi, whereas Ag does not embrittle the boundary in agreement with experiment. While we reject the prevailing view that "electronic" effects (i.e., charge transfer) are responsible for embrittlement, we do not exclude the role of chemistry. However, numerical results show a striking equivalence between the alkali metal Na and the semimetal Bi, small differences being accounted for by their contrasting "size" and "softness" (defined here). In order to separate structural and chemical effects unambiguously if not uniquely, we model the embrittlement process by taking the system of grain boundary and free surfaces through a sequence of precisely defined gedanken processes; each of these representing a putative mechanism. We thereby identify three mechanisms of embrittlement by substitutional impurities, two of which survive in the case of embrittlement or cohesion enhancement by interstitials. Two of the three are purely structural and the third contains both structural and chemical elements that by their very nature cannot be further unraveled. We are able to take the systems we study through each of these stages by explicit computer simulations and assess the contribution of each to the net reduction in intergranular cohesion. The conclusion we reach is that embrittlement by both Bi and Na is almost exclusively structural in origin; that is, the embrittlement is a size effect.

Boron in copper: A perfect misfit in the bulk and cohesion enhancer at a grain boundary

Using first principles electronic structure methods, we calculate the effects of boron impurities in bulk copper and at surfaces and grain boundaries. We find that boron segregation to the Sigma5(310)[001] grain boundary should strengthen the boundary up to 1.5 ML coverage (15.24 at./nm2). The maximal effect is observed at 0.5 ML and corresponds to boron atoms filling exclusively grain boundary interstices. In copper bulk, B causes significant distortion both in interstitial and regular lattice sites, for which boron atoms are either too big or too small. The distortion is compensated to a large extent when the interstitial and substitutional boron combine together to form a strongly bound dumbbell. Our prediction is that bound boron impurities should appear in a sizable proportion if not dominate in most experimental conditions. A large discrepancy between calculated heats of solution and experimental terminal solubility of B in Cu is found, indicating either a significant failure of the density functional approach or, more likely, strongly overestimated solubility limits in the existing B-Cu phase diagram.

A Van der Pol-Mathieu equation for the dynamics of dust grain charge in dusty plasmas

The chaotic profile of dust grain dynamics associated with dust-acoustic oscillations in a dusty plasma is considered. The collective behaviour of the dust plasma component is described via a multi-fluid model, comprising Boltzmann distributed electrons and ions, as well as an equation of continuity possessing a source term for the dust grains, the dust momentum and Poisson's equations. A Van der Pol–Mathieu-type nonlinear ordinary differential equation for the dust grain density dynamics is derived. The dynamical system is cast into an autonomous form by employing an averaging method. Critical stability boundaries for a particular trivial solution of the governing equation with varying parameters are specified. The equation is analysed to determine the resonance region, and finally numerically solved by using a fourth-order Runge–Kutta method. The presence of chaotic limit cycles is pointed out.

Theoretical analysis on microwave heating of oil–water emulsions supported on ceramic, metallic or composite plates

A detailed theoretical analysis has been carried out to study efficient heating due to microwaves for one-dimensional (1D) oil–water emulsion samples placed on various ceramic, metallic (reflective) and ceramic–metallic composite supports. Two typical emulsion systems are considered such as oil-in-water (o/w) and water-in-oil (w/o). A preliminary study has been carried out via average power vs emulsion thickness diagram to estimate microwave power absorption within emulsion samples for various cases. The maxima in average power, also termed as ‘resonances’, are observed for specific emulsion thicknesses and the two consecutive resonances of significant magnitudes are termed as R1 and R2 modes. For both o/w and w/o emulsions, it is observed that microwave power absorption is enhanced in presence of metallic and composite supports during both R1 and R2 modes. The efficient heating strategies characterized by ‘large heating rates’ with ‘minimal thermal runaway’ i.e. uniform temperature distributions within the sample have been assessed for each type of emulsion. Based on the detailed spatial distributions of power and temperature for various cases, SiC-metallic composite support may be recommended as an optimal heating strategy for o/w samples with higher oil fractions (0.45) whereas metallic and Alumina-metallic composite supports may be favored for samples with smaller oil fractions (=0.3) during R1 mode. For w/o samples, SiC-metallic composite support may be suitable heating strategy for all ranges of water fractions during R1 mode. During R2 mode, metallic and Alumina-metallic composite supports are favored for both o/w and w/o emulsion samples. Current study recommends the efficient way to use microwaves in a single mode waveguide and the heating strategy can be suitably extended for heating of any other emulsions for which dielectric properties are easily measurable or available in the literature.

High-solid-content hydroxyapatite slurry for the production of bone substitute scaffolds

Key to various bone substitute scaffold production techniques is the development of free-flowing ceramic slurry with optimum theological properties. The aim is to achieve a colloidal suspension with as high a solid content as possible while maintaining a low viscosity which easily penetrates the pores of relevant sacrificial templates. The following investigation describes the optimization of a hydroxyapatite slip and demonstrates its potential application in scaffold production. Using predominantly spherical particles of hydroxyapatite of between 0.82 mu m and 16.2 mu m, coupled with a 2 wt % addition of the anionic polyelectrolyte, ammonium polyacrylate, an 80 wt % (55.9 vol %) hydroxyapatite solid loaded slip with a viscosity of approximately 126 mPa s has been developed. Its ability to infiltrate and replicate porous preforms has been shown using polyurethane foam. The enhanced particle packing achieved has allowed for the production of scaffolds with highly dense and uniform grain structures. The results represent a significant improvement in current slurry production techniques and can be utilized to develop high-density ceramic bone substitute scaffolds.

Silica grain labelling and EDX spectroscopy; evidence for inter-grain diffusion of Pt(NH3)(4)(2+) species during Pt/SiO2 catalyst preparation by ionic exchange

Labelling of silica grains and energy dispersive X-ray spectroscopy (EDX) in a TEM-FEG (field emission gun) were used to demonstrate the migration of Pt(NH3)(4)(2+) species from one grain to another during Pt/SiO2 catalyst preparation by the ion-exchange procedure.