Reactive growth

Metal oxidation is a heterogeneous solid state reaction and starts in the same way as other heterogeneous reactions with nucleation and initial growth. This was discussed in Chapter 6. A time-dependent nucleation rate may dominate the overall growth kinetics of thin Films. Even under an optical microscope (i.e., in macroscopic dimensions), preferential sites of growth can still be discerned [J. Benard (1971)). This indicates that lateral transport on the surface (e.g., at sites where screw dislocations emerge) can possibly be more important for the initial reactive growth than transport across thin oxide layers. 

Chapters 6 and 7 dealt with solid state reactions in which the product separates the reactants spatially. For binary (or quasi-binary) systems, reactive growth is the only mode possible for an isothermal heterogeneous solid state reaction if local equilibrium prevails and phase transitions are disregarded. In ternary (and higher) systems, another reactive growth mode can occur. This is the internal reaction mode. The reaction product does not form at the contacting surfaces of the two reactants as discussed in Chapters 6 and 7, but instead forms within the interior of one of the reactants or within a solvent crystal. 

Fig. 6.62 Reactive growth of an oxide layer by metal oxydation (see text) [334],...

Since faults are zones of inherent weakness they may be reactivated over geologic time. Usually, faulting occurs well after the sediments have been deposited. An exception to this is a growth feu/f (also termed a syn-sedimentary fault), shown in Figure 5.7. They are extensional structures and can frequently be observed on seismic sections through deltaic sequences. The fault plane is curved and in a three dimensional view has the shape of a spoon. This type of plane is called listric. Growth faults can be visualised as submarine landslides caused by rapid deposition of large quantities of water-saturated... 

Madey and co-workers followed the reduction of titanium with XPS during the deposition of metal overlayers on TiOi [87]. This shows the reduction of surface TiOj molecules on adsorption of reactive metals. Film growth is readily monitored by the disappearance of the XPS signal from the underlying surface [88, 89]. This approach can be applied to polymer surfaces [90] and to determine the thickness of polymer layers on metals [91]. Because it is often used for chemical analysis, the method is sometimes referred to as electron spectroscopy for chemical analysis (ESCA). Since x-rays are very penetrating, a grazing incidence angle is often used to emphasize the contribution from the surface atoms. 

To see why the assumption of equal reactivity is so important to step-growth polymers, recall from Table 1.2 the kind of chemical reactions which produce typical condensation polymers ... 

As with polyesters, the amidation reaction of acid chlorides may be carried out in solution because of the enhanced reactivity of acid chlorides compared with carboxylic acids. A technique known as interfacial polymerization has been employed for the formation of polyamides and other step-growth polymers, including polyesters, polyurethanes, and polycarbonates. In this method the polymerization is carried out at the interface between two immiscible solutions, one of which contains one of the dissolved reactants, while the second monomer is dissolved in the other. Figure 5.7 shows a polyamide film forming at the interface between an aqueous solution of a diamine layered on a solution of a diacid chloride in an organic solvent. In this form interfacial polymerization is part of the standard repertoire of chemical demonstrations. It is sometimes called the nylon rope trick because of the filament of nylon produced by withdrawing the collapsed film. 

In ionic polymerizations termination by combination does not occur, since all of the polymer ions have the same charge. In addition, there are solvents such as dioxane and tetrahydrofuran in which chain transfer reactions are unimportant for anionic polymers. Therefore it is possible for these reactions to continue without transfer or termination until all monomer has reacted. Evidence for this comes from the fact that the polymerization can be reactivated if a second batch of monomer is added after the initial reaction has gone to completion. In this case the molecular weight of the polymer increases, since no new growth centers are initiated. Because of this absence of termination, such polymers are called living polymers. 

Chain-Growth Associative Thickeners. Preparation of hydrophobically modified, water-soluble polymer in aqueous media by a chain-growth mechanism presents a unique challenge in that the hydrophobically modified monomers are surface active and form micelles (50). Although the initiation and propagation occurs primarily in the aqueous phase, when the propagating radical enters the micelle the hydrophobically modified monomers then polymerize in blocks. In addition, the hydrophobically modified monomer possesses a different reactivity ratio (42) than the unmodified monomer, and the composition of the polymer chain therefore varies considerably with conversion (57). The most extensively studied monomer of this class has been acrylamide, but there have been others such as the modification of PVAlc. Pyridine (58) was one of the first chain-growth polymers to be hydrophobically modified. This modification is a post-polymerization alkylation reaction and produces a random distribution of hydrophobic units. 

The requirements of thin-film ferroelectrics are stoichiometry, phase formation, crystallization, and microstmctural development for the various device appHcations. As of this writing multimagnetron sputtering (MMS) (56), multiion beam-reactive sputter (MIBERS) deposition (57), uv-excimer laser ablation (58), and electron cyclotron resonance (ECR) plasma-assisted growth (59) are the latest ferroelectric thin-film growth processes to satisfy the requirements. 

An example of a commercial semibatch polymerization process is the early Union Carbide process for Dynel, one of the first flame-retardant modacryhc fibers (23,24). Dynel, a staple fiber that was wet spun from acetone, was introduced in 1951. The polymer is made up of 40% acrylonitrile and 60% vinyl chloride. The reactivity ratios for this monomer pair are 3.7 and 0.074 for acrylonitrile and vinyl chloride in solution at 60°C. Thus acrylonitrile is much more reactive than vinyl chloride in this copolymerization. In addition, vinyl chloride is a strong chain-transfer agent. To make the Dynel composition of 60% vinyl chloride, the monomer composition must be maintained at 82% vinyl chloride. Since acrylonitrile is consumed much more rapidly than vinyl chloride, if no control is exercised over the monomer composition, the acrylonitrile content of the monomer decreases to approximately 1% after only 25% conversion. The low acrylonitrile content of the monomer required for this process introduces yet another problem. That is, with an acrylonitrile weight fraction of only 0.18 in the unreacted monomer mixture, the low concentration of acrylonitrile becomes a rate-limiting reaction step. Therefore, the overall rate of chain growth is low and under normal conditions, with chain transfer and radical recombination, the molecular weight of the polymer is very low. 

HydroxyethyUiydrazine (11) is a plant growth regulator. It is also used to make a coccidiostat, furazoHdone, and has been proposed, as has (14), as a stabilizer in the polymerization of acrylonitrile (72,73). With excess epoxide, polysubstitution occurs and polyol chains can form to give poly(hydroxyaLkyl) hydrazines which have been patented for the preparation of cellular polyurethanes (74) and as corrosion inhibitors for hydrauHc fluids (qv) (75). DialkyUiydrazines, R2NNH2, and alkylene oxides form the very reactive amineimines (15) which react further with esters to yield aminimides (16) ... 

The nuclear chain reaction can be modeled mathematically by considering the probable fates of a typical fast neutron released in the system. This neutron may make one or more coUisions, which result in scattering or absorption, either in fuel or nonfuel materials. If the neutron is absorbed in fuel and fission occurs, new neutrons are produced. A neutron may also escape from the core in free flight, a process called leakage. The state of the reactor can be defined by the multiplication factor, k, the net number of neutrons produced in one cycle. If k is exactly 1, the reactor is said to be critical if / < 1, it is subcritical if / > 1, it is supercritical. The neutron population and the reactor power depend on the difference between k and 1, ie, bk = k — K closely related quantity is the reactivity, p = bk jk. i the reactivity is negative, the number of neutrons declines with time if p = 0, the number remains constant if p is positive, there is a growth in population. 

The properties of polymers formed by the step growth esterification (1) of glycols and dibasic acids can be manipulated widely by the choice of coreactant raw materials (Table 1) (2). The reactivity fundamental to the majority of commercial resins is derived from maleic anhydride [108-31-6] (MAN) as the unsaturated component in the polymer, and styrene as the coreactant monomer. Propylene glycol [57-55-6] (PG) is the principal glycol used in most compositions, and (i9f2v (9)-phthahc anhydride (PA) is the principal dibasic acid incorporated to moderate the reactivity and performance of the final resins. 

Studies have shown that, in marked contrast to carbanionic polymerisation, the reactivity of the free oxonium ion is of the same order of magnitude as that of its ion pair with the counterion (6). On the other hand, in the case of those counterions that can undergo an equiUbrium with the corresponding covalent ester species, the reactivity of the ionic species is so much greater than that of the ester that chain growth by external attack of monomer on covalent ester makes a negligible contribution to the polymerisation process. The relative concentration of the two species depends on the dielectric constant of the polymerisation medium, ie, on the choice of solvent. 

Step-growth polymerization is characterized by the fact that chains always maintain their terminal reactivity and continue to react together to form longer chains as the reaction proceeds, ie, a -mer + -mer — (a + )-mer. Because there are reactions that foUow this mechanism but do not produce a molecule of condensation, eg, the formation of polyurethanes from diols and diisocyanates (eq. 6), the terms step-growth and polycondensation are not exactly synonymous (6,18,19). 

Mesitylene continues to be of considerable iaterest as a research chemical. Its ttilateral stmcture, extremely high reactivity for electrophilic reactions, and the fact that large suppHes are available poiat to good growth potential. 

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