Nucleation modification

Modifications to Precipitates. Silicon is sometimes added to Al—Cu—Mg alloys to help nucleate S precipitates without the need for cold work prior to the elevated temperature aging treatments. Additions of elements such as tin [7440-31-5] Sn, cadmium [7440-43-9] Cd, and indium [7440-74-6] In, to Al—Cu alloys serve a similar purpose for 9 precipitates. Copper is often added to Al—Mg—Si alloys in the range of about 0.25% to 1.0% Cu to modify the metastable precursor to Mg2Si. The copper additions provide a substantial strength increase. When the copper addition is high, the quaternary Al CuMg Si Q-phase must be considered and dissolved during solution heat treatment. 

Carbon black is also used as a pigment for paints and printing inks, as a nucleation agent in weather modifications, and as a solar energy absorber. About 70% of the worlds consumption of carbon black is used in the production of tires and tire products. Approximately 20% goes into other products such as footwear, belts, hoses, etc. and the rest is used in such items as paints, printing ink, etc. The world capacity of carbon black was approximately 17 billion pounds in 1998. U.S. projected consumption for the year 2003 is approximately 3.9 billion pounds. 

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 nucleation rate onto a crystal is determined by the flux onto an ensemble of substrates. As the nuclei should be widely separated for the nucleation approach to be valid, this does not appear to be unreasonable. However, the subsequent way in which this flux is used to determine the thickness and growth rate seems somewhat inconsistent as explained below. However, a modification of the derivations would satisfy this query, and it is not likely that this will greatly affect the results. 

The model described in Sect. 3.5.1 is a very crude representation of a true three-dimensional lamella, and over the years modifications have been applied in order to make it more realistic. The major assumptions, however, are still inherent in all of them, that is, the deposition of complete stems is controlled by rate constants which obey Eq. (3.83). No other reaction paths are allowed and the growth rate is then given by nucleation and spreading formulae. We do not give the details of the calculations which are very similar, but more complicated, than those already given. Rather, we try to provide an overview of the work which has been done. Most of this has been mentioned already elsewhere in this review. 

Kinetic expressions for appropriate models of nucleation and diffusion-controlled growth processes can be developed by the methods described in Sect. 3.1, with the necessary modification that, here, interface advance obeys the parabolic law [i.e. is proportional to (Dt),/2]. (This contrasts with the linear rate of interface advance characteristic of decomposition reactions.) Such an analysis has been provided by Hulbert [77], who considers the possibilities that nucleation is (i) instantaneous (0 = 0), (ii) constant (0 = 1) and (iii) deceleratory (0 < 0 < 1), for nuclei which grow in one, two or three dimensions (X = 1, 2 or 3, respectively). All expressions found are of the general form... 

First-order phase transitions exhibit hysteresis, i.e. the transition takes place some time after the temperature or pressure change giving rise to it. How fast the transformation proceeds also depends on the formation or presence of sites of nucleation. The phase transition can proceed at an extremely slow rate. For this reason many thermodynamically unstable modifications are well known and can be studied in conditions under which they should already have been transformed. 

It has been proposed that Glu-61 could alternately act as a ligand to the ferroxidase site and to the nucleation site, and hence serve as a go-between to move iron (eventually in both directions) from one site to another (Lawson et al, 1991). What is clear is that modification of both the ferroxidase centre and the nucleation centre leads to ferritins which do not oxidize or incorporate iron (Wade et al, 1991 Sun et al, 1993). 

It seems also meaningful to recall that, for both PVL and iPP, the metastable chiral modification is not obtained from solution. This fact is hard to rationalize if polymorphic discrimination occurs on the basis of the secondary nucleation site which should exist also in the presence of the solution it rather points to diffusion and to transport problems in the melt, or thermodynamic control in solution. 

Copper phthalocyanine pigments also demonstrate good overall stability to organic solvents. A number of solvents, however, especially aromatics, may cause a change of modification in unstable types or overcrystallization in stable varieties. This phenomenon is largely due to the tendency of the stable phase to nucleate. The particle size of the resulting cystals decreases as the number of nuclei rises. (3-Copper Phthalocyanine Blue is the thermodynamically stable modification. 

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