Noncrystallinity

The otiier type of noncrystalline solid was discovered in the 1980s in certain rapidly cooled alloy systems. D Shechtman and coworkers [15] observed electron diffraction patterns with sharp spots with fivefold rotational synnnetry, a syimnetry that had been, until that time, assumed to be impossible. It is easy to show that it is impossible to fill two- or tliree-dimensional space with identical objects that have rotational symmetries of orders other than two, tliree, four or six, and it had been assumed that the long-range periodicity necessary to produce a diffraction pattern with sharp spots could only exist in materials made by the stacking of identical unit cells. The materials that produced these diffraction patterns, but clearly could not be crystals, became known as quasicrystals. 

Toby B FI and Egami T 1992 Accuracy of pair distribution function analysis applied to crystalline and noncrystalline materials Aota Crystaiiogr.k 48 336-46... 

Due to the noncrystalline, nonequilibrium nature of polymers, a statistical mechanical description is rigorously most correct. Thus, simply hnding a minimum-energy conformation and computing properties is not generally suf-hcient. It is usually necessary to compute ensemble averages, even of molecular properties. The additional work needed on the part of both the researcher to set up the simulation and the computer to run the simulation must be considered. When possible, it is advisable to use group additivity or analytic estimation methods. 

Structure and Bonding in Noncrystalline Solids G. E. Walrafen, A. G. Revesz, Eds., Plenum, New York (1986). 

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. 

Noncrystalline domains in fibers are not stmctureless, but the stmctural organization of the polymer chains or chain segments is difficult to evaluate, just as it is difficult to evaluate the stmcture of Hquids. No direct methods are available, but various combinations of physicochemical methods such as x-ray diffraction, birefringence, density, mechanical response, and thermal behavior, have been used to deduce physical quantities that can be used to describe the stmcture of the noncrystalline domains. Among these quantities are the amorphous orientation function and the amorphous density, which can be related to some of the important physical properties of fibers. 

The description of the atomic distribution in noncrystalline materials employs a distribution function, (r), which corresponds to the probability of finding another atom at a distance r from the origin atom taken as the point r = 0. In a system having an average number density p = N/V, the probability of finding another atom at a distance r from an origin atom corresponds to Pq ( ). Whereas the information given by (r), which is called the pair distribution function, is only one-dimensional, it is quantitative information on the noncrystalline systems and as such is one of the most important pieces of information in the study of noncrystalline materials. The interatomic distances cannot be smaller than the atomic core diameters, so = 0. 

Chromate conversion coatings are thin, noncrystalline, adherent surface layers of low solubiHty phosphoms and/or chromium compounds produced by the reaction of suitable reagents with the metal surface (2,3). The two classes of chromate coatings are chromium phosphates (green chromates) and chromium chromates (gold chromates). 

Noncrystalline aromatic polycarbonates (qv) and polyesters (polyarylates) and alloys of polycarbonate with other thermoplastics are considered elsewhere, as are aHphatic polyesters derived from natural or biological sources such as poly(3-hydroxybutyrate), poly(glycoHde), or poly(lactide) these, too, are separately covered (see Polymers, environmentally degradable Sutures). Thermoplastic elastomers derived from poly(ester—ether) block copolymers such as PBT/PTMEG-T [82662-36-0] and known by commercial names such as Hytrel and Riteflex are included here in the section on poly(butylene terephthalate). Specific polymers are dealt with largely in order of volume, which puts PET first by virtue of its enormous market volume in bottie resin. 

Noncrystalline Silicas. The noncrystalline forms of silica iaclude bulk vitreous silica and a variety of other amorphous types, which are of substantial commercial importance (see SiLiCA, AMORPHOUS SILICA SiLiCA, VITREOUS SILICA). A review discussiag the occurrence, synthesis, properties, and apphcations of the various forms of silica adsorbents is available (71). 

Thermal Properties. Spider dragline silk was thermally stable to about 230°C based on thermal gravimetric analysis (tga) (33). Two thermal transitions were observed by dynamic mechanical analysis (dma), one at —75° C, presumed to represent localized mobiUty in the noncrystalline regions of the silk fiber, and the other at 210°C, indicative of a partial melt or a glass transition. Data from thermal studies on B. mori silkworm cocoon silk indicate a glass-transition temperature, T, of 175°C and stability to around 250°C (37). The T for wild silkworm cocoon silks were slightly higher, from 160 to 210°C. 

Maltitol (4-0-a-D-glucopyranosyl-D-glucitol) formed by catalytic hydrogenation of maltose (97), has been obtained both as a noncrystalline powder and a viscous Hquid (98). Stmctures of disacchatide alcohols are shown ia Figure 3. 

The melting temperature, T, of PVDC is independent of molecular weight above DP = 100. However, as shown in Eigure 2, it drops sharply at lower molecular weights. Below the hexamer, the products are noncrystalline Hquids. 

The nmr spectmm of PVAc iu carbon tetrachloride solution at 110°C shows absorptions at 4.86 5 (pentad) of the methine proton 1.78 5 (triad) of the methylene group and 1.98 5, 1.96 5, and 1.94 5, which are the resonances of the acetate methyls iu isotactic, heterotactic, and syndiotactic triads, respectively. Poly(vinyl acetate) produced by normal free-radical polymerization is completely atactic and noncrystalline. The nmr spectra of ethylene vinyl acetate copolymers have also been obtained (33). The ir spectra of the copolymers of vinyl acetate differ from that of the homopolymer depending on the identity of the comonomers and their proportion. 

At low relative humidities, adsorption is due to interaction of water with accessible hydroxyl groups. These are present on the lignin and on the carbohydrates ia the noncrystalline or poorly crystalline regions. The high differential heat of adsorption by dry wood, - 1.09 kJ/g (469 Btu/lb) water. 

Diffraction of x-rays from many atoms with many electrons results in a two-dimensional continuous pattern of peaks and valleys. Diffraction from a hquid or an amorphous (noncrystalline) soHd results in a continuous pattern with few features, mainly broad peaks and valleys. 

The term glass has two meanings, ie, the material and a state of matter. The glassy or vitreous condition is where the atoms of the material have a random orientation. This amorphous or noncrystalline nature leads to physical properties typical of the product caHed glass, including unpredictable breaks, no sharp melting temperature, and no heat of fusion. 

The solubihty of random copolymers of monomers whose homopolymers are noncrystalline also varies quite regularly as the relative amounts of the comonomers are changed. The solubihty of random copolymers is often low in solvents for the respective homopolymers but high in solvent pairs (51). 

Several other catalyst systems have been suggested, including boron fluoride and both crystalline and noncrystalline siUcas and alurninosihcates. Although no commercial faciUty exists, the concept of using a crystalline siUca or alurninosihcate catalyst in an integral reaction and distillation apparatus has been proposed (9). 

Physically there are differences. Like all polymeric fibers nylon contains crystalline and noncrystalline areas. Only amino groups ia the noncrystalline regioas are accessible. 

Benzamidomethyl-A -methylcysteine has been prepared as a crystalline derivative (H0CH2NHC0C6H 5, anhydr. CF3CO2H, 25°, 45 min, 88% yield as the tri-fluoroacetate salt) and cleaved (100% yield) by treatment with mercury(II) acetate (pH 4, 25°, 1 h) followed by hydrogen sulfide. Attempted preparation of S-acetamidomethyl-N-methylcysteine resulted in noncrystalline material, shown by TLC to be a mixture. ... 

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