Aggregative nucleation

Polyacrylics are produced by copolymerizing acrylonitrile with other monomers such as vinyl acetate, vinyl chloride, and acrylamide. Solution polymerization may be used where water is the solvent in the presence of a redox catalyst. Free radical or anionic initiators may also be used. The produced polymer is insoluble in water and precipitates. Precipitation polymerization, whether self nucleation or aggregate nucleation, has been reviewed by Juba. The following equation is for an acrylonitrile polymer initiated by a free radical ... 

Once the oligomers have formed, two mechanisms, self-nucleation and aggregate nucleation, are used to describe particle nucleation. 

In aggregate nucleation the oligomers reversibly associate with each other until the aggregate reaches a critical size above which it is thermodynamically stable and continues to grow. 

Brune H 1998 Microscopic view of epitaxial metal growth nucleation and aggregation Surf. Sc . Rep. 31 121... 

Additives, whether hydrophobic solutes, other surfactants or polymers, tend to nucleate micelles at concentrations lower than in the absence of additive. Due to this nucleating effect of polymers on micellization there is often a measurable erne, usually called a critical aggregation concentration or cac, below the regular erne observed in the absence of added polymer. This cac is usually independent of polymer concentration. The size of these aggregates is usually smaller than that of free micelles, and this size tends to be small even in the presence of added salt (conditions where free micelles tend to grow in size). 

Fig. 5. Protein folding. The unfolded polypeptide chain coUapses and assembles to form simple stmctural motifs such as -sheets and a-hehces by nucleation-condensation mechanisms involving the formation of hydrogen bonds and van der Waal s interactions. Small proteins (eg, chymotrypsin inhibitor 2) attain their final (tertiary) stmcture in this way. Larger proteins and multiple protein assembhes aggregate by recognition and docking of multiple domains (eg, -barrels, a-helix bundles), often displaying positive cooperativity. Many noncovalent interactions, including hydrogen bonding, van der Waal s and electrostatic interactions, and the hydrophobic effect are exploited to create the final, compact protein assembly. Further stmctural...

Polypropylene molecules repeatedly fold upon themselves to form lamellae, the sizes of which ate a function of the crystallisa tion conditions. Higher degrees of order are obtained upon formation of crystalline aggregates, or spheruHtes. The presence of a central crystallisation nucleus from which the lamellae radiate is clearly evident in these stmctures. Observations using cross-polarized light illustrates the characteristic Maltese cross model (Fig. 2b). The optical and mechanical properties ate a function of the size and number of spheruHtes and can be modified by nucleating agents. Crystallinity can also be inferred from thermal analysis (28) and density measurements (29). 

Cry staUization at temperatures of about 40°C results in heavy nucleation and a fine product. At temperatures above 75°C, only cry stal growth occurs, giving rise to large, weU-cry staUized aggregates composed of hexagonal rods and prisms (Fig. 2a). 

Thus under ideal circumstances the modes of aggregation can be discriminated by such plots. Deviations below the expected slopes are usually attributed to collision inefficiency leading to imperfect aggregation. In a crystallization or precipitation process, of course, deviations may also occur due to growth and nucleation unless properly accounted for. 

Hounslow, M.J., 1990b. Nucleation, growth and aggregation rates from steady-state experimental data. American Institution of Chemical Engineers Journal, 36, 1748-1753. 

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