Density nucleation

The effect of a second polymer blended with PPS which causes enhanced nucleation of PPS has been previously observed. It was found that low concentrations (1—2 wt %) of poly(phenylene sulfide ketone) and poly(ether ether ketone), when melt-blended with PPS, function effectively to increase the nucleation density of PPS (149). 

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. 

Recently Butler et al. [4] reported the deposition of nanocrystalline diamond films with the conventional deposition conditions for micrometer-size polycrystalline diamond films. The substrate pretreatment by the deposition of a thin H-terminated a-C film, followed by the seeding of nanodiamond powder, increased the nucleation densities to more than 10 /cm on a Si substrate. The resultant films were grown to thicknesses ranging from 100 nm to 5 fim, and the thermal conductivity ranged from 2.5 to 12 W/cm K. 

The models incorporate two microscopic parameters, the site density and the critical nucleus size. A fit of experimental current transients to the models allows conclusions, for example, concerning the effect of additives on nucleation rate. Fabricus et al. found by analysis of current transients that thiourea increases the nucleation density of copper deposited on glassy carbon at low concentration, but decreases it at higher concentration [112], Schmidt et al. found that Gold nucleation on pyrolytic graphite is limited by the availability of nucleation sites [113], Nucleation density and rate were found to depend on applied potential as was the critical nucleus size. Depending on concentration, critical nuclei as small as one atom have been estimated from current transient measurements. Michailova et al. found a critical nucleus of 11 atoms for copper nucleation on platinum [114], These numbers are typical, and they are comparable to the thermodynamic critical radii [86],... 

We suggest that both the lamellar and the microfibrillar morphologies are formed by a nucleation and growth process. A low nucleation density of crystal solvates results in a lamellar morphology, whereas a high nucleation density of the crystalline PBT results in formation of microfibrils. 

Marsh (1988), Cashman and Marsh (1988), and Cashman and Ferry (1988) investigated the application of crystal size distribution (CSD) theory (Randolph and Larson, 1971) to extract crystal growth rate and nucleation density. The following summary is based on the work of Marsh (1988). In the CSD method, the crystal population density, n(L), is defined as the number of crystals of a given size L per unit volume of rock. The cumulative distribution function N(L) is defined as... 

Chronoamperometric experiments on zinc electroreduction on GC from acetate solutions showed that the nucleation density increases with increase of temperature [44]. M oreover, the nucleation rate constant is always very large, equal to 1.41 x 10 s . This indicates that the mechanism of zinc electrodeposition on the GC electrode follows a three-dimensional instantaneous nucleation and growth model within the controlled temperature range. 

The same mechanism of zinc electrodeposition on the GC electrode was observed in sulfate, chloride, and acetate ion solutions [227]. The anions mainly affected the nucleation densities during zinc deposition, which resulted in a different surface morphology. The nucleation rate constant was the same in the chloride and sulfate solutions and was equal to 1.22 x 10 s h In the presence of acetate and chloride ions, the deposited zinc film tends to grow in a multilayered pattern, while in sulfate solution, the zinc deposition forms irregular grains. A new approach to the estimation of zinc electrocrystallization parameters on the GC electrode from acetate solutions was described by Yu et al. [228]. 

The homogeneous nucleation of martensite in typical solids is too slow by many orders of magnitude to account for observed results. Calculations of typical values of AQc using the classical nucleation model of Section 19.1.4 (see Exercise 19.3) yield values greatly exceeding 76 kT. Furthermore, nearly all martensitic transformations commence at very sparsely distributed sites. Small-particle experiments [14] have yielded typical nucleation densities on the order of one nucleation event per 50 pm diameter Fe-Ni alloy powder particle.3 Thus, nucleation of martensite is believed to occur at a small number of especially potent heterogeneous nucleation sites. 

The number of PPE particles dispersed in the SAN matrix, i.e., the potential nucleation density for foam cells, is a result of the competing mechanisms of dispersion and coalescence. Dispersion dominates only at rather small contents of the dispersed blend phase, up to the so-called percolation limit which again depends on the particular blend system. The size of the dispersed phase is controlled by the processing history and physical characteristics of the two blend phases, such as the viscosity ratio, the interfacial tension and the viscoelastic behavior. While a continuous increase in nucleation density with PPE content is found below the percolation limit, the phase size and in turn the nucleation density reduces again at elevated contents. Experimentally, it was found that the particle size of immiscible blends, d, follows the relation d --6 I Cdispersed phase and C is a material constant depending on the blend system. Subsequently, the theoretical nucleation density, N , is given by... 

It should be noted that the transition is not a prompt as described, but smooth. Nevertheless, an optimum content of the dispersed phase exists for each blend system, where the potential nucleation density approaches its maximum. The... 

Fig. 12 Nucleation density of foamed PPE/SAN blends vs number of theoretically available nucleation sites (=particle density of the PPE phase). The dotted lines represent the theoretical nucleation density at different phase sizes of PPE (reprinted from [47])...

For evaluating the efficiency of the nanostructured interface for cell nucleation, the particle density of PPE, as a measure for the number of nucleating sites available for nucleation, is plotted versus the nucleation density observed for the foam (Fig. 21). For comparison, the previously found values of the uncompatibilized PPE/SAN blend are added. For PPE/SAN, even the relatively high number of PPE particles of around 5 x 10ncm-3 only leads to nucleation of approximately 2.5 x 1010 cells cm-3, i.e., only 1/20 of the potentially available PPE particles act as cell nucleating agents. Via compatibilization, however, not only the particle density of PPE and the nucleation density can be increased, but also the efficiency is strongly enhanced. While the number of cells directly scales with particle density, more than two foam cells are nucleated by one PPE particle. 

In order to explain this effect, two phenomena can be hypothesized (1) multiple nucleation of the PPE phases, and (2) break-up the PPE phase and, subsequently an increase of the particle density. Discussing the latter case first, it can be estimated that the time scale for dispersion is not sufficiently high [3, 83]. Therefore, multiple nucleation is likely to induce the higher nucleation densities, making SBM an ideal candidate for nucleation by interfacial effects. 

Fig. 21 Nucleation density vs particle density of PPE/SAN blends compatibilized by SMB triblock terpolymers, in comparison to uncompatibilized PPE/SAN blends...

Fig. 34 (a) Mean cell size and (b) nucleation density as function of the SBM content of the (PPE/PS)/SAN/SBM blend systems (foaming temperature 180°C, foaming time 10 s)... 

Fig. 36 Cell size and nucleation density as reported in literature, and comparison with the results observed in this study. The lines indicate the relative foam density, as theoretically calculated...

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