Growth surface nucleation

Fig. 2. Devitrification rate of vitreous siUca for surface-nucleated cristobahte as a function of temperature (99). Growth rate is proportional to the square...

A number of theories have been put forth to explain the mechanism of polytype formation (30—36), such as the generation of steps by screw dislocations on single-crystal surfaces that could account for the large number of polytypes formed (30,35,36). The growth of crystals via the vapor phase is beheved to occur by surface nucleation and ledge movement by face specific reactions (37). The soHd-state transformation from one polytype to another is beheved to occur by a layer-displacement mechanism (38) caused by nucleation and expansion of stacking faults in close-packed double layers of Si and C. 

Models used to describe the growth of crystals by layers call for a two-step process (/) formation of a two-dimensional nucleus on the surface and (2) spreading of the solute from the two-dimensional nucleus across the surface. The relative rates at which these two steps occur give rise to the mononuclear two-dimensional nucleation theory and the polynuclear two-dimensional nucleation theory. In the mononuclear two-dimensional nucleation theory, the surface nucleation step occurs at a finite rate, whereas the spreading across the surface is assumed to occur at an infinite rate. The reverse is tme for the polynuclear two-dimensional nucleation theory. Erom the mononuclear two-dimensional nucleation theory, growth is related to supersaturation by the equation. 

One of the more important uses of OM is the study of crystallization growth rates. K. Cermak constructed an interference microscope with which measurements can be taken to 50° (Ref 31). This app allows for study of the decompn of the solution concentrated in close proximity to the growing crystal of material such as Amm nitrate or K chlorate. In connection with this technique, Stein and Powers (Ref 30) derived equations for growth rate data which allow for correct prediction of the effects of surface nucleation, surface truncation in thin films, and truncation by neighboring spherulites... 

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]. 

As shown in 4.4.1., two stages usually occur in surface nucleation, nucleation and then nuclei growth. If surface nucleation is fast (Model C) it is likely due to reaction of a gas with the solid particle. The reaction of a liquid is the other possibility, i.e.-... 

Massive barite crystals (type C) are also composed of very fine grain-sized (several xm) microcrystals and have rough surfaces. Very fine barite particles are found on outer rims of the Hanaoka Kuroko chimney, while polyhedral well-formed barite is in the inner side of the chimney (type D). Type D barite is rarely observed in black ore. These scanning electron microscopic observations suggest that barite precipitation was controlled by a surface reaction mechanism (probably surface nucleation, but not spiral growth mechanism) rather than by a bulk diffusion mechanism. 

Layadi et al. have shown, using in. situ spectroscopic ellipsometry, that both surface and subsurface processes are involved in the formation of /xc-Si [502, 503]. In addition, it was shown that the crystallites nucleate in the highly porous layer below the film surface [502, 504], as a result of energy released by chemical reactions [505, 506] (chemical annealing). In this process four phases can be distinguished incubation, nucleation, growth, and steady state [507]. In the incubation phase, the void fraction increases gradually while the amorphous fraction decreases. Crystallites start to appear when the void fraction reaches a maximum... 

When the attachment of the substrate to the precipitate to be formed is strong, the clusters tend to spread themselves out on the substrate and form thin surface islands. A special limiting case is the formation of a surface nucleus on a seed crystal of the same mineral (as in surface nucleation crystal growth). As the cohesive bonding within the cluster becomes stronger relative to the bonding between the cluster and the substrate, the cluster will tend to grow three-dimensionally (Steefel and Van Cappellen, 1990). 

Surface nucleation and the surface spiral mechanism are parallel mechanisms. Consequently the growth rate will be equal to the sum of the rates of these two mechanisms, and in extreme cases approximately equal to the rate of the faster one among them. 

We have reviewed today s knowledge of the mechanisms for growth of electrolyte crystals from aqueous solution Convection, diffusion, and adsorption ( ) mechanisms leading to linear rate laws, as well as the surface spiral mechanism (parabolic rate law) and surface nucleation (exponential rate law). All of these mechanisms may be of geochemical importance in different situations. 

Tanabe and Kamasaki (52) observed the nucleation growth mechanism in the deposition of Au on Fe(OOl) and Fe(l 10) single crystals. The population of nuclei (TDCs) of Au electrodeposited in the initial stages of deposition was 3 X 10 cm . In further deposition, micro-TDCs were connected one to another forming a network structure. Stable coherent deposits of Au were formed when the surface coverage was about 80%. 

In situ dynamic ETEM studies in controlled environments of oxide catalysts permit direct observations of redox pathways under catalytic reaction conditions and provide a better fundamental understanding of the nucleation, growth and the nature of defects at the catalyst surface and their role in catalysis (Gai 1981-1982 92). The following paragraphs describe the methods of observation and quantitative analyses of the surface and microstmctural changes of the catalyst, and correlation of microstmctural data with measurements of catalytic reactivity. We examine examples of pure shear and crystallographic (CS) shear defects that occur under catalytic conditions. 

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