Nucleation at surfaces

Miich effort in recent years has been aimed at modelling nucleation at surfaces and several excellent reviews exist [20, 21 and 22]. Mean-field nucleation theory is one of these models and has a simple picture at its core. 

The nucleation behavior of transition metal particles is determined by the ratio between the thermal energy of the diffusing atoms and the interaction of the metal atoms at the various nucleation sites. To create very small particles or even single atoms, low temperatures and metal exposures have to be used. The metal was deposited as metal atoms impinging on the surface. The metal exposure is given as the thickness (in monolayer ML) of a hypothetical, uniform, close-packed metal layer. The interaction strength of the metals discussed here was found to rise in the series from Pd < Rh < Co ( Ir) < V [17,32]. Whereas Pd and Rh nucleate preferentially at line defects at 300 K and decorate the point defects at 90 K, point defects are the predominant nucleation center for Co and V at 300 K. At 60 K, Rh nucleates at surface sites between point defects [16,33]. 

Westwater (W4, W5) has written a detailed review of boiling in liquids with emphasis on nucleation at surfaces. Although written in 1956, this is still very useful and it provides a detailed description of the factors affecting nucleation. In a more recent review, Leppert and Pitts (L2) have described the important factors in nucleate boiling and bubble growth, and Bankoff (B2) has reviewed the field of diffusion-controlled bubble growth in nonflowing batch systems. 

Stacking faults growth (nucleation at surface and neck region of particles) gamma powder and thin film (4,5)... 

Introduction of the surface-nucleation mechanism in numerical computation of elastic-plastic wave evolution leads to enhanced precursor attenuation in thin specimens, but not in thicker ones. Inclusion of dislocation nucleation at subgrain boundaries indicates that a relatively low concentration of subgrain boundaries ( 2/mm) and nucleation density (10"-10 m ) is sufficient to obtain predicted precursor decay rates which are comparable to those obtained from the experiments. These experiments are only slightly above the threshold necessary to produce enhanced elastic-precursor decay. 

A new, low-pressure, plasma-assisted proeess for synthesising diamonds has been found by Roy et al [83,84]. An intimate mixture of various forms of carbon with one of many metals (e.g., Au, Ag, Fe, Cu, Ni) is exposed to a microwave plasma derived from pure hydrogen at temperatures ranging from 600-1000 °C. Roy et al postulate a mechanism in which a solid solution of atomic hydrogen and the metal. Me, facilitates dissolution of carbon to form molten droplets of Me -Cj,-H. Diamonds nucleate at the surface of the droplets as the temperature is reduced. 

Figure 6.2. Sloichiomclric CuPl, ordered at 550°C for 157 hours. Viewed under polarised light in reflection. Shows growth of ordered domains, heterogeneously nucleated at grain boundaries and surface scratches (after Irani and Cahn 197.5).

The following two pictures (Figure 6.2-8a and b) were acquired at h-500 mV and at -I-450 mV vs. Cu/Cu and show that at h-450 mV vs. Cu/Cu monolayer high Cu clusters nucleate at the steps between different Au terraces. Thus, the pair of shoulders in the cyclic voltammogram is correlated with this surface process. 

Reactions of the general type A + B -> AB may proceed by a nucleation and diffusion-controlled growth process. Welch [111] discusses one possible mechanism whereby A is accepted as solid solution into crystalline B and reacts to precipitate AB product preferentially in the vicinity of the interface with A, since the concentration is expected to be greatest here. There may be an initial induction period during solid solution formation prior to the onset of product phase precipitation. Nuclei of AB are subsequently produced at surfaces of particles of B and growth may occur with or without maintained nucleation. 

Dehydration reactions are typically both endothermic and reversible. Reported kinetic characteristics for water release show various a—time relationships and rate control has been ascribed to either interface reactions or to diffusion processes. Where water elimination occurs at an interface, this may be characterized by (i) rapid, and perhaps complete, initial nucleation on some or all surfaces [212,213], followed by advance of the coherent interface thus generated, (ii) nucleation at specific surface sites [208], perhaps maintained during reaction [426], followed by growth or (iii) (exceptionally) water elimination at existing crystal surfaces without growth [62]. 

Hill et al. [117] extended the lower end of the temperature range studied (383—503 K) to investigate, in detail, the kinetic characteristics of the acceleratory period, which did not accurately obey eqn. (9). Behaviour varied with sample preparation. For recrystallized material, most of the acceleratory period showed an exponential increase of reaction rate with time (E = 155 kJ mole-1). Values of E for reaction at an interface and for nucleation within the crystal were 130 and 210 kJ mole-1, respectively. It was concluded that potential nuclei are not randomly distributed but are separated by a characteristic minimum distance, related to the Burgers vector of the dislocations present. Below 423 K, nucleation within crystals is very slow compared with decomposition at surfaces. Rate measurements are discussed with reference to absolute reaction rate theory. 

Second, the molecular orientation of the fiber and the prepolymer matrix is important. The rate of crystal nucleation at the fiber-matrix interface depends on the orientation of matrix molecules just prior to their change of phase from liquid to solid. Thus, surface-nucleated morphologies are likely to dominate the matrix stmcture. 

Fig.1 Schematic representation of the different nucleation sites on the alumina film Mid nucleation at line defects, Mpd nucleation at point defects, Mrs nucleation at regular surface sites...

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