Nucleation investigations

Onset of Nucleation. Investigations of initial moments of nucleation using a stopped flow technique revealed that the nuclei formation may be preceded by the formation of complexes of the reacting species as precursors of nuclei (Tanaka and Iwasaki 1983, 1985). The lifetime of precursors depends on the concentration ratio of the reacting species, and is on the order of 60-500 ms for AgBr. Even for simple 1-1 electrolytes, the reaction of particle formation may involve two or more stages. 

There is also another type of primary nucleation called self-nucleation investigated first by Blundell et al. (1966). The foreign surfaces for self-nucleation are provided by crystals of the same species which survived during thermal history. Since there is no extra surface free energy change during self-nucleation, it is also called athermal nucleation. This type of nucleation is an important source of memory effects for polymer crystallization. 

An important approach to the study of nucleation of solids is the investigation of small droplets of large molecular clusters. Years ago, Turnbull showed that by studying small droplets one could eliminate impurities in all except a few droplets and study homogeneous nucleation at significant undercoolings [13]. 

Various appHcations such as lubricant additives, dyes, pigments, and catalysts are under investigation. Tungsten can be deposited from tungsten hexacarbonyl, but carbide formation and gas-phase nucleation present serious problems (1,2). As a result, tungsten halides are the preferred starting material. 

The size-dependent agglomeration kernels suggested by both Smoluchowski and Thompson fit the experimental data very well. For the case of a size-independent agglomeration kernel and the estimation without disruption (only nucleation, growth and agglomeration), the least square fits substantially deviate from the experimental data (not shown). For this reason, further investigations are carried out with the theoretically based size-dependent kernel suggested by Smoluchowski, which fitted the data best ... 

The properties of water near ionic salt surfaces are of interest not only for the understanding of the mechanism of dissolution processes but also for the understanding of the chemistry in the atmosphere next to oceans [205]. Experiments in UHV [205-208] indicate that the water-covered NaCl surface is quite stable at low temperatures. An early simulation study by Anastasiou et al. [209] focused on the arrangements and orientations of water molecules in contact with a rigid NaCl crystal. Ohtaki and coworkers investigated the dissolution of very small cubic crystals of NaF, KF, CsF, LiCl, NaCl, and KCl [210] and the nucleation [211] of NaCl and CsF in a... 

The electrodeposition of Ag has also been intensively investigated [41 3]. In the chloroaluminates - as in the case of Cu - it is only deposited from acidic solutions. The deposition occurs in one step from Ag(I). On glassy carbon and tungsten, three-dimensional nucleation was reported [41]. Quite recently it was reported that Ag can also be deposited in a one-electron step from tetrafluoroborate ionic liquids [43]. However, the charge-transfer reaction seems to play an important role in this medium and the deposition is not as reversible as in the chloroaluminate systems. 

N2. Noel, M. B., Experimental investigation of the forced convection and nucleate boiling heat transfer characteristics of liquid ammonia, JPL Tech. Rept. No. 32-125 (July 1961). 

The layout of this article is as follows Section 2 considers the equilibrium aspects of the crystals whilst Sects. 3 and 4 explain the growth theories, divided into nucleation and non-nucleation theories, respectively. Finally, Sect. 5 provides an overview and suggests future lines of investigation. 

Growth theories of surfaces have received considerable attention over the last sixty years as summarized by Laudise et al. [53] and Jackson [54]. The well-known model of the crystal surface incorporating adatoms, ledges and kinks was first introduced by Kossel [55] and Stranski [56]. Becker and Doring [57] calculated the rates of nucleation of new layers of atoms, and Papapetrou [58] investigated dendritic crystallization. 

Although specific calculations for i and g are not made until Sect. 3.5 onwards, the mere postulate of nucleation controlled growth predicts certain qualitative features of behaviour, which we now investigate further. First the effect of the concentration of the polymer in solution is addressed - apparently the theory above fails to predict the observed concentration dependence. Several modifications of the model allow agreement to be reached. There should also be some effect of the crystal size on the observed growth rates because of the factor L in Eq. (3.17). This size dependence is not seen and we discuss the validity of the explanations to account for this defect. Next we look at twin crystals and any implications that their behaviour contain for the applicability of nucleation theories. Finally we briefly discuss the role of fluctuations in the spreading process which, as mentioned above, are neglected by the present treatment. 

The importance of twinned crystals in demonstrating that nucleation is the relevant growth mechanism has been realized since 1949 [64, 99]6. They were first investigated extensively in polymer crystals by Blundell and Keller [82] and they have recently received increased attention as a means of establishing, or otherwise, the nucleation postulate for lamellar growth [90, 91, 95,100-102]. The diversity of opinion in the literature shows that it is very difficult to draw definite conclusions from the experimental evidence, and the calculations are often founded upon implicit assumptions which may or may not be justified. We therefore restrict our discussion to an introduction to the problem, the complicating features which make any a priori assumptions difficult, and the remaining information which may be fairly confidently deduced. 

A drastic departure from nucleation theory was made by Sadler [44] who proposed that the crystal surface was thermodynamically rough and a barrier term arises from the possible paths a polymer may take before crystallizing in a favourable configuration. His simulation and models have shown that this would give results consistent with experiments. The two-dimensional row model is not far removed from Point s initial nucleation barrier, and is practically identical to a model investigated by Dupire [35]. Further comparison between the two theories would be beneficial. 

The high sensitivity of the MS [160] makes it a particularly appropriate tool for the investigation of nucleation and growth processes, since it is possible to measure rates during the early part of the reaction using small samples or individual crystals. The influence of residual gases [160] on the initiation of reaction can also be determined. Short scan times enable very rapid reactions e.g. detonations, to be studied, and it is also possible to measure simultaneously the rate of evolution of several different product molecules. 

Some limitations of optical microscopy were apparent in applying [247—249] the technique to supplement kinetic investigations of the low temperature decomposition of ammonium perchlorate (AP), a particularly extensively studied solid phase rate process [59]. The porous residue is opaque. Scanning electron microscopy showed that decomposition was initiated at active sites scattered across surfaces and reaction resulted in the formation of square holes on m-faces and rhombic holes on c-faces. These sites of nucleation were identified [211] as points of intersection of line dislocations with an external boundary face and the kinetic implications of the observed mode of nucleation and growth have been discussed [211]. 

The characteristic feature of solid—solid reactions which controls, to some extent, the methods which can be applied to the investigation of their kinetics, is that the continuation of product formation requires the transportation of one or both reactants to a zone of interaction, perhaps through a coherent barrier layer of the product phase or as a monomolec-ular layer across surfaces. Since diffusion at phase boundaries may occur at temperatures appreciably below those required for bulk diffusion, the initial step in product formation may be rapidly completed on the attainment of reaction temperature. In such systems, there is no initial delay during nucleation and the initial processes, perhaps involving monomolec-ular films, are not readily identified. The subsequent growth of the product phase, the main reaction, is thereafter controlled by the diffusion of one or more species through the barrier layer. Microscopic observation is of little value where the phases present cannot be unambiguously identified and X-ray diffraction techniques are more fruitful. More recently, the considerable potential of electron microprobe analyses has been developed and exploited. 

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. 

Cyclic voltammetry is most commonly used to investigate the polymerization of a new monomer. Polymerization and film deposition are characterized by increasing peak currents for oxidation of the monomer on successive cycles, and the development of redox waves for the polymer at potentials below the onset of monomer oxidation. A nucleation loop, in which the current on the reverse scan is higher than on the corresponding forward scan, is commonly observed during the first cycle.56,57 These features are all illustrated in Fig. 3 for the polymerization of a substituted pyrrole.58... 

Although the mechanisms discussed above are still topics of debate, it is now firmly established that the electrodeposition of conducting polymers proceeds via some kind of nucleation and phase-growth mechanism, akin to the electrodeposition of metals.56,72-74 Both cyclic voltammetry and potential step techniques have been widely used to investigate these processes, and the electrochemical observations have been supported by various types of spectroscopy62,75-78 and microscopy.78-80... 

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