Amorphous region

Polymers are difficult to model due to the large size of microcrystalline domains and the difficulties of simulating nonequilibrium systems. One approach to handling such systems is the use of mesoscale techniques as described in Chapter 35. This has been a successful approach to predicting the formation and structure of microscopic crystalline and amorphous regions. 

Attention must also be focused on the noncrystalline domains. Many important properties of fibers can be directly related to these noncrystalline or amorphous regions. For example, absorption of dyes, moisture, and other penetrants occurs in these regions. These penetrants are not expected to diffuse into the crystalline domains, although there may be adsorption on crystaUite surfaces. The extensibUity and resUience of fibers is also directly associated with the noncrystalline regions. 

Standard polyester fibers contain no reactive dye sites. PET fibers are typically dyed by diffusiag dispersed dyestuffs iato the amorphous regions ia the fibers. Copolyesters from a variety of copolymeri2able glycol or diacid comonomers open the fiber stmcture to achieve deep dyeabiHty (7,28—30). This approach is useful when the attendant effects on the copolyester thermal or physical properties are not of concern (31,32). The addition of anionic sites to polyester usiag sodium dimethyl 5-sulfoisophthalate [3965-55-7] has been practiced to make fibers receptive to cationic dyes (33). Yams and fabrics made from mixtures of disperse and cationicaHy dyeable PET show a visual range from subde heather tones to striking contrasts (see Dyes, application and evaluation). 

The dissipation factor (the ratio of the energy dissipated to the energy stored per cycle) is affected by the frequency, temperature, crystallinity, and void content of the fabricated stmcture. At certain temperatures and frequencies, the crystalline and amorphous regions become resonant. Because of the molecular vibrations, appHed electrical energy is lost by internal friction within the polymer which results in an increase in the dissipation factor. The dissipation factor peaks for these resins correspond to well-defined transitions, but the magnitude of the variation is minor as compared to other polymers. The low temperature transition at —97° C causes the only meaningful dissipation factor peak. The dissipation factor has a maximum of 10 —10 Hz at RT at high crystallinity (93%) the peak at 10 —10 Hz is absent. 

Transitions. Samples containing 50 mol % tetrafluoroethylene with ca 92% alternation were quenched in ice water or cooled slowly from the melt to minimise or maximize crystallinity, respectively (19). Internal motions were studied by dynamic mechanical and dielectric measurements, and by nuclear magnetic resonance. The dynamic mechanical behavior showed that the CC relaxation occurs at 110°C in the quenched sample in the slowly cooled sample it is shifted to 135°C. The P relaxation appears near —25°C. The y relaxation at — 120°C in the quenched sample is reduced in peak height in the slowly cooled sample and shifted to a slightly higher temperature. The CC and y relaxations reflect motions in the amorphous regions, whereas the P relaxation occurs in the crystalline regions. The y relaxation at — 120°C in dynamic mechanical measurements at 1 H2 appears at —35°C in dielectric measurements at 10 H2. The temperature of the CC relaxation varies from 145°C at 100 H2 to 170°C at 10 H2. In the mechanical measurement, it is 110°C. There is no evidence for relaxation in the dielectric data. 

PVF displays several transitions below the melting temperature. The measured transition temperatures vary with the technique used for measurement. T (L) (lower) occurs at —15 to —20 " C and is ascribed to relaxation free from restraint by crystallites. T (U) (upper) is in the 40 to 50°C range and is associated with amorphous regions under restraint by crystallites (63). Another transition at —80° C has been ascribed to short-chain amorphous relaxation and one at 150°C associated with premelting intracrystalline relaxation. 

The plasticizer content of a polymer may be increased by the suppression of crystallization in the polymer, but if crystallization subsequently occurs the plasticizer exudes. For highly crystalline resins, the small amounts of plasticizer allowable can change the nature of the small amorphous regions with a consequent overall change in properties. 

Effect of Fiber Properties. Acid dyes are attracted to the accessible amine ends of the nylon chains located in the amorphous regions of the fiber. Acid dye affinity of nylon can be adjusted by a dding excess diamine or diacid to the polymer salt or by changing the molecular weight in polymerization. A light acid-dyeable nylon-6,6 is spun with 15—20 amine ends, expressed in terms of gram equivalents per 10 g of polymer. A medium or... 

At strains over 300% the stress occurs mostiy in the amorphous regions up to the point where the sample breaks. AH of the grades exhibit permanent set, and the curves of grades with a Shore Hardness of 55 and higher exhibit a yield point. This means that parts have to be designed for low strains to stay within the area of elastic recovery. Special grades of elastomer are available to provide hydrolysis resistance (194), improved heat aging (195), and improved uv-stabihty (196). 

This unusual behavior results from unsolvated crystalline regions in the PVC that act as physical cross-links. These allow the PVC to accept large amounts of solvent (plasticizers) in the amorphous regions, lowering its T to well below room temperature, thus making it mbbery. PVC was, as a result, the first thermoplastic elastomer (TPE). This mbber-like material has stable properties over a wide temperature range (32,138—140). 

Cellulose is the main component of the wood cell wall, typically 40—50% by weight of the dry wood. Pure cellulose is a polymer of glucose residues joined by 1,4-P-glucosidic bonds. The degree of polymerization (DP) is variable and may range from 700 to 10,000 DP or more. Wood cellulose is more resistant to dilute acid hydrolysis than hemiceUulose. X-ray diffraction indicates a partial crystalline stmcture for wood cellulose. The crystalline regions are more difficult to hydrolyze than the amorphous regions because removal of the easily hydrolyzed material has Htde effect on the diffraction pattern. 

Treatment of ceUulose with acids results in preferential hydrolysis in the more accessible amorphous regions and produces a product known as microcrystalline ceUulose (MCC). MCC is used to prepare fat-free or reduced-fat food products, to strengthen and stabilize food foams, as a tableting aid, and as a noncalotic bulking agent for dietetic foods. It has GRAS status. 

As is typical for crystalline polymers incapable of specific interactions with liquids, there are no solvents at room temperature but liquids which have a similar solubility parameter (8 = 22.4 MPa ) will cause a measure of swelling, principally in the amorphous region. ... 

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