Solids Reactive Systems

An alternative approach is a two 100%-solids system which can be blended under agitation and have a sufficiently long pot life (8-16 h) so that it can be coated using conventional knife-coating techniques. Curing at 150°C for, say, 2 min gives a track-free coating. 

Also possible is a 100%-solids heat-curable foam which can be direct- or transfer-coated with the standard knife or reverse roll coaters. By incorporation of a blowing agent, the urethane coating is foamed during the oven curing. It is normally used with a conventional top coat. 

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In recent years, the use of solvent-borne adhesives has been seriously restricted. Solvents are, in general, volatile, flammable and toxic. Further, solvent may react with other airborne contaminants contributing to smog formation and workplace exposure. These arguments have limited the use of solvent-bome adhesives by different national and European regulations. Although solvent recovery systems and afterburners can be effectively attached to ventilation equipment, many factories are switching to the use of water-borne rubber adhesives, hot melts or 100% solids reactive systems, often at the expense of product performance or labour efficiency. 

Mass transfer with chemical reaction in multiphase systems" covers, indeed, a large area. Table 1 shows a general classification of the systems encountered. From the possible two-phase systems, solid-solid reactions, liquid-solid (reactive or catalytic) and gas-solid (reactive or catalytic) reactions are not discussed here. The first one was reviewed by Tamhankar and Doraiswamy (2) and gas-solid (reactive) systems, such as, coal gasification, calcination of limestone, reduction of ores, etc. have been treated in some detail in recent reviews (3-5). The industrially important fluid-solid catalytic processes were the topic of a previous Advanced Study Institute (6) and have been also discussed authoritatively elsewhere (5,7). Concerning solid (reactive)-liquid two-phase systems, only some interesting examples are presented in Table 2 (1). 

Thermoplastic linear polyurethanes which are usually chain-terminated so that no unreacted free NCO groups remain available. Environmental considerations direct growing attention to these newer non-polluting urethane adhesive forms, e.g. powders, films, aqueous dispersions and 100% solids reactive systems. Some systems do possess blocked diisocyanates which are activated on heating to produce chemically reactive solid systems. 

Currently, waterborne adhesives are being introduced into the shoe industry. Their performance is quite similar to that of the solvent-borne adhesives, so it can be estimated that for several years they will be used in shoe industry. However, the future seems to be directed through the use of moisture-curing holt-melt urethane and thermoplastic urethane adhesives as they are 100% solid reactive systems and evaporation of solvents is not necessary. Although hot-melt urethanes could replace solvent-borne adhesives, this could take longer to occur because of the vastly different equipment requirements and the change in bonding concept by the shoe manufacturers. 

This chapter is restricted to homogeneous, single-phase reactions, but the restriction can sometimes be relaxed. The formation of a second phase as a consequence of an irreversible reaction will not affect the kinetics, except for a possible density change. If the second phase is solid or liquid, the density change will be moderate. If the new phase is a gas, its formation can have a major effect. Specialized models are needed. Two-phase ffows of air-water and steam-water have been extensively studied, but few data are available for chemically reactive systems. 

Instead of applying synthetic methods to alter chromophore reactivity, this new way of controlling chemical reactivity involves choosing an appropriate solid micellar system (from the available multitude) and exploiting it to manipulate the chemistry of the entrapped compound. The sol-gel matrix and the micellar solubilization, in fact, have a synergetic effect. Their combination produces effects stronger and more tuneable than in solution, so that a careful selection of sol-gel entrapped surfactants allows one to induce enormous changes in the dopant properties. 

Carboxylated polymers can be prepared by mechanical treatment of frozen polymer solutions in acrylic acid (Heinicke 1984). The reaction mechanism is based on the initiation of polymerization of the frozen monomer by free macroradicals formed during mechanolysis of the starting polymer. Depending on the type of polymer, mixed, grafted, and block polymers with a linear or spatial structure are obtained. What is important is that the solid-phase reaction runs with a relatively high rate. For instance, in the polyamide reactive system with acrylic acid, the tribochemical reaction leading to the copolymer is completed after a treatment time of 60 s. As a rule, the mechanical activation of polymers is mainly carried out in a dry state, because the structural imperfections appear most likely here. 

For species present as gases in the actual reactive system, the standard state is the pure ideal gas at pressure P°. For liquids and solids, it is usually the state of pure real liquid or solid at P°. The standard-state pressure P° is fixed at 100 kPa. Note that the standard states may represent different physical states for different species any or all of the species may be gases, liquids, or solids. 

Sonochemistry can be roughly divided into categories based on the nature of the cavitation event homogeneous sonochemistry of liquids, heterogeneous sonochemistry of liquid—liquid or liquid—solid systems, and sonocatalysis (which ovedaps the first two) (12—15). In some cases, ultrasonic irradiation can increase reactivity by neady a million-fold (16). Because cavitation can only occur in liquids, chemical reactions are not generally seen in the ultrasonic irradiation of solids or solid-gas systems. 

Dynamic mechanical analysis methods are frequently used to investigate polymerization and curing processes in reactive systems. These methods allow us to obtain both relative and absolute rheological characteristics of a material. Measurements can be made in both the fluid and solid states without affecting the inherent structure of the polymerizing system. 

A typical evolution of equilibrium mechanical properties during reaction is shown in Fig. 6.1. The initial reactive system has a steady shear viscosity that grows with reaction time as the mass-average molar mass, Mw, increases and it reaches to infinity at the gel point. Elastic properties, characterized by nonzero values of the equilibrium modulus, appear beyond the gel point. These quantities describe only either the liquid (pregel) or the solid (postgel) state of the material. Determination of the gel point requires extrapolation of viscosity to infinity or of the equilibrium modulus to zero. 

A correlation between surface and volume processes is described in Section 5. The atomic-molecular kinetic theory of surface processes is discussed, including processes that change the solid states at the expense of reactions with atoms and molecules of a gas or liquid phase. The approach reflects the multistage character of the surface and volume processes, each stage of which is described using the theory of chemical kinetics of non-ideal reactive systems. The constructed equations are also described on the atomic level description of diffusion of gases through polymers and topochemical processes. 

For a reaction with positive gas mole change, Eq. (47) indicates that Kx decreases with pressure. Because ce is a monotonically increasing function of Kx, the equilibrium extent of a reaction with positive Avgas always decreases as pressure is increased. This is an example of Le Chatelier s principle, which states that a reaction at equilibrium shifts in response to a change in external conditions in a way that moderates the change. In this case, because the reaction increases the number of moles of gas and thus the pressure, the reaction shifts back to reactants. The isothermal compressibility of a reactive system can, therefore, be much greater than that of a nonreactive system. This effect can be dramatic in systems with condensed phases. For example, in the calcium carbonate dissociation discussed in Example 12, if the external pressure is raised above the dissociation pressure of C02, the system will compress down to the volume of the solid. Of course, a similar effect is observed in simple vaporization or sublimation equilibrium. As the pressure on water at 100°C is increased above 1.0 atm, all vapor is removed from the system. 

Although both diagrams appear similar at first glance, there are some important differences. In particular, in the reactive system all solid lines intersect at the origin. The dotted lines are parallel and change their orientation at the bisection line. Furthermore, the pathgrid of the reactive system is symmetric with respect to the bisection line due to the fact that both enantiomers behave the same. This topology has important implications for the construction of wave solutions as discussed in detail in Ref. [13]. 

Figures VI and VII illustrate the initial viscosity of both the Hycar 2103 and Hycar 2106 systems as well as the viscosity increase with time due to the reactive nature of the 2-component system. These figures will help in determining the percent solids necessary for processing on a given piece of equipment depending upon its viscosity handling capability. Since the 100% solids PSA systems have high initial viscosities of over 100 Pa s (100,000 cps), the conventional knife-over-roll and reverse roll coaters can not process them.

In most liquid- and solid-phase systems, the dilute approximation is typically invalid, and, as a result, many body effects play a significant role. Many body effects are manifested through the effect of solvent or catalyst on reactivity and through concentration-dependent reaction rate parameters. Under these conditions, the one-way coupling is inadequate, and fully coupled models across scales are needed, i.e., two-way information traffic exists. This type of modeling is the most common in chemical sciences and will be of primary interest hereafter. In recent papers the terms multiscale integration hybrid, parallel, dynamic,... 

Figure 2.27. Capillary rise in a reactive solid / liquid system due to the formation of a wettable reaction...

In the first Section, attention is paid to distinguishing between reactive and non-reactive systems from the point of view of wettability. Then, after describing wetting and bonding of non-reactive couples, we discuss the effect on these characteristics of oxygen, which is the most common impurity in solid/liquid/vapour systems, as well as the effect of reactive and non-reactive alloying elements. Finally, in a short Section, we consider some results for the wetting of fluorides which like oxides are very ionic. 

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