Cross-linking general

PVA can be prepared by chemical or physical cross-linking general methods for chemical cross-linking are the use of chemical cross-linkers or the use of electron beams or y-... 

However, the fast physical aging limits the practical application of PTMSP membranes. One solution is the cross-linking of PTMSP, which stabilizes the large excess free volume elements and hence improves physical stability [86-88]. Cross-linking generally reduces gas permeability due to free volume reduction, while the polymer network becomes more size selective and gas selectivity increases. 

With low-density foams, the relationships of physical properties to structure are very complex because of the wide variation of cell structures possible. Polyurethane foams are probably the most versatile of all. They are capable of being made rigid or flexible, and with open or closed cells. Foam rigidity is controlled by the degree of cross-linking, generally based on the type and concentration of trifunctional reactants in the formulation. 

The selection of the type of peroxide determines the speed of cross-linking. Generally, peroxyketals are faster curing than dialkyl peroxides, as indicated by the lower temperatures required for a 10 min cure in Table 13.1. 

Polymers will be elastic at temperatures that are above the glass-transition temperature and below the liquiflcation temperature. Elasticity is generally improved by the light cross linking of chains. This increases the liquiflcation temperature. It also keeps the material from being permanently deformed when stretched, which is due to chains sliding past one another. Computational techniques can be used to predict the glass-transition and liquiflcation temperatures as described below. 

Commercially produced elastic materials have a number of additives. Fillers, such as carbon black, increase tensile strength and elasticity by forming weak cross links between chains. This also makes a material stilfer and increases toughness. Plasticizers may be added to soften the material. Determining the effect of additives is generally done experimentally, although mesoscale methods have the potential to simulate this. 

Natural rubber, cis-1,4-polyisoprene, cross-linked with sulfur. This reaction was discovered by Goodyear in 1839, making it both historically and commercially the most important process of this type. This reaction in particular and crosslinking in general are also called vulcanization. 

We might be tempted to equate the forces given by Eqs. (9.61) and (3.38) and solve for a from the resulting expression. However, Eq. (3.38) is not suitable for the present problem, since it was derived for a cross-linked polymer stretched in one direction with no volume change. We are concerned with a single, un-cross-linked molecule whose volume changes in a spherically symmetrical way. The precursor to Eq. (3.36) in a more general derivation than that presented in Chap. 3 is... 

Acid-C t lyzed Chemistry. Acid-catalyzed reactions form the basis for essentially all chemically amplified resist systems for microlithography appHcations (61). These reactions can be generally classified as either cross-linking (photopolymerization) or deprotection reactions. The latter are used to unmask acidic functionality such as phenohc or pendent carboxyhc acid groups, and thus lend themselves to positive tone resist apphcations. Acid-catalyzed polymer cross-linking and photopolymerization reactions, on the other hand, find appHcation in negative tone resist systems. Representative examples of each type of chemistry are Hsted below. 

Laboratory tests indicated that gamma radiation treatment and cross-linking using triaHylcyanurate or acetylene produced a flexible recycled plastic from mixtures of polyethylene, polypropylene, general-purpose polystyrene, and high impact grade PS (62). 

The reactions are catalyzed by tertiary amines, quaternary ammonium salts, metal salts, and basic ion-exchange resins. The products are difficult to purify and generally contain low concentrations of acryhc acid and some diester which should be kept to a minimum since its presence leads to product instabihty and to polymer cross-linking. 

Elastomeric Modified Adhesives. The major characteristic of the resins discussed above is that after cure, or after polymerization, they are extremely brittie. Thus, the utility of unmodified common resins as stmctural adhesives would be very limited. Eor highly cross-linked resin systems to be usehil stmctural adhesives, they have to be modified to ensure fracture resistance. Modification can be effected by the addition of an elastomer which is soluble within the cross-linked resin. Modification of a cross-linked resin in this fashion generally decreases the glass-transition temperature but increases the resin dexibiUty, and thus increases the fracture resistance of the cured adhesive. Recendy, stmctural adhesives have been modified by elastomers which are soluble within the uncured stmctural adhesive, but then phase separate during the cure to form a two-phase system. The matrix properties are mosdy retained the glass-transition temperature is only moderately affected by the presence of the elastomer, yet the fracture resistance is substantially improved. 

Polymer-based rocket propellants are generally referred to as composite propellants, and often identified by the elastomer used, eg, urethane propellants or carboxy- (CTPB) or hydroxy- (HTPB) terrninated polybutadiene propellants. The cross-linked polymers act as a viscoelastic matrix to provide mechanical strength, and as a fuel to react with the oxidizers present. Ammonium perchlorate and ammonium nitrate are the most common oxidizers used nitramines such as HMX or RDX may be added to react with the fuels and increase the impulse produced. Many other substances may be added including metallic fuels, plasticizers, stabilizers, catalysts, ballistic modifiers, and bonding agents. Typical components are Hsted in Table 1. 

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