Amorphous cross-linked polymer

Lignin is an amorphous, cross-linked polymer network consisting of an irregular array of variously bonded hydroxy- and methoxy-substituted phenylpropane units [13]. The chemical structure varies depending on its source. Lignin is less polar than cellulose and acts as a chemical adhesive within and between fibers. 

In the most general sense, an elastomer may be defined as an amorphous, cross-linked polymer above its glass transition temperature (see Section 8.12). The two terms rubber and elastomer mean nearly the same thing. The term rubber comes from the rubbing out action of an eraser. Originally, of course, rubber was natural rubber, c -polyisoprene. The term elastomer is more general and refers to the elastic-bearing properties of the materials. 

When an amorphous cross-linked polymer above Tg is deformed and released, it snaps back with rubbery characteristics. The dependence of the stress necessary to deform the elastomer depends on the cross-link density, elongation, and temperature in a way defined by statistical thermodynamics. 

The ultraphosphates are situated between P O q and the metaphosphates. These comparatively Htde-known, highly cross-linked polymers contain at least some of the phosphoms atoms as triply coimected branching points. This stmctural feature is quite unstable toward hydrolysis. Ultraphosphates undergo rapid decomposition upon dissolution. In amorphous ultraphosphates, the cross-linking is presumably scattered randomly throughout the stmctural matrix in contrast, crystalline ultraphosphates have a regular pattern. 

As will be seen from curves A, B and C of Figure 9.1, the softening point of an amorphous polymer, i.e. the temperature at which the modulus drops catastrophically, is closely associated with the T. (Such softening does not of course occur in highly cross-linked polymers, as in type D, unless degradation also takes place.)... 

Later we will describe both oxidation and reduction processes that are in agreement with the electrochemically stimulated conformational relaxation (ESCR) model presented at the end of the chapter. In a neutral state, most of the conducting polymers are an amorphous cross-linked network (Fig. 3). The linear chains between cross-linking points have strong van der Waals intrachain and interchain interactions, giving a compact solid [Fig. 14(a)]. By oxidation of the neutral chains, electrons are extracted from the chains. At the polymer/solution interface, positive radical cations (polarons) accumulate along the polymeric chains. The same density of counter-ions accumulates on the solution side. 

A chemical cross-hnking of MEEP was obtained by Shriver [606] by using polyethylene glycol (PEG) dialkoxide, which also forms polymer salt complexes. The cross-linked polymers were prepared by substituting a part (1 and 10 mole%) of the methoxyethoxyethoxy ethanol by PEG in the synthesis of MEEP. Contrary to the MEEP, the amorphous polymers obtained do not flow and are stable even at 140 °C. The maximum ionic conductivity at 30 °C, obtained after complexation with liSOjCFj, are 4.1x10" S cm for MEEP/PEG 1% complexed with 6.4 wt% salt and 3x10" S cm for MEEP/PEG 10% com-plexed with 8.9 wt% salt. These values are comparable with those obtained with the parent hnear polyphosphazenes. 

The temperature dependence of the compliance and the stress relaxation modulus of crystalline polymers well above Tf is greater than that of cross-linked polymers, but in the glass-to-rubber transition region the temperature dependence is less than for an amorphous polymer. A factor in this large temperature dependence at T >> TK is the decrease in the degree of Crystallinity with temperature. Other factors arc the reciystallization of strained crystallites ipto unstrained ones and the rotation of crystallites to relieve the applied stress (38). All of these effects occur more rapidly as the temperature is raised. 

Crystalline polymers are much less soluble than amorphous polymers at temperatures below the melting point (Tm). Cross-linked polymers may swell but will not dissolve. 

We have chosen to focus on the molecular variables that influence fatigue resistance in a stress cracking environment molecular weight, chain regularity, and molecular parameters of the medium. In most cases, we will differentiate between amorphous, crystalline, and cross-linked polymers. In a subsequent section we will examine the impact of sample preparation on the fatigue resistance sterilization, cross Unking, orientation. Another section will focus on the different strategies to improve the ESCR. 

Fig. 11-13. Effect of frequency on dynamic response of an amorphous, lighlly cross-linked polymer (a) elastic behavior at high frequency—stress and strain are in phase, (b) liquid-like behavior at low frequency—stress and strain are 90" out of phase, and (c) general case—stress and strain are out of phase.

The polymer molecules may occur as long unbranched straight chains (linear polymers), branched chains, or a three-dimensional lattice work where the branches link the main chains together (i.e. cross-linked polymers). Properties of plastic vary according to their form of molecular structure. Materials may also be amorphous or crystalline, where the latter are generally less permeable. The degree of crystallinity is usually established by X-ray diffraction studies. 

Tobolsky and Takahashi (7,8) showed that large concentrations of S8 can remain dissolved in a liquid condition in other polymers. In many cases these compositions appear completely stable, i.e., there is no tendency for the dissolved sulfur to crystallize out. The best example is cross-linked polyethylene tetrasulfide polymers which can retain 40% of dissolved sulfur in the form of liquid S8 over long periods of time. The sulfur was shown to be S8 by quantitatively extracting it with carbon disulfide. It was demonstrated that the specific volume of the dissolved sulfur plotted against temperature fits smoothly with the data of specific volume of molten sulfur vs. temperature and finally that the mechanical properties of the cross-linked polymers containing dissolved sulfur are just what would be expected from plasticized, cross-linked, amorphous polymers. Ellis (9) reported the use of resins made by the interaction of 2,3-xylenol and sulfur monochloride as sulfur additives. These resins were added to three times their weight of molten sulfur. There was no indication of sulfur crystallization in the resultant material, which also... 

Lignins. Lignins are amorphous, cross-linked phenolic polymers that occur uniquely in vascular plants and comprise 20-30% of most wood. Lignins isolated from wood are polydisperse, with molecular weights in the range of thousands to hundreds of thousands (4). Lignins are produced almost exclusively from three cinnamyl alcohols, whose structures are shown in Chart I. These structural units have propylphenyl carbon skeletons and differ... 

---