Crystallinity in nylon

Nylon. The high degree of crystallinity in nylon means that plasticization can occur only at very low levels. Plasticizers are used in nylon but are usually sulfonamide based since these are generally more compatible than phthalates. DEHP is 25 phr compatible other phthalates less so. Sulfonamides are compatible up to 50 phr. 

The low temperature ( 140°C) anionic ring opening polymerization is further complicated by the crystallinity in nylon 6. Magill [66] has reported that the temperature for maximum crystallization rate in nylon 6 is about 140-145°C. The nucleation rate is low above 145°C, whereas viscous effects hinder crystal growth below this temperature. As a result, at about 140-145°C, heterogeneous reaction conditions can be encountered (as we have seen in our studies) if there is simultaneous polymerization of caprolactam and crystallization of the nylon 6 formed. 

The chemical structure of a polymer determines whether it will be crystalline or amorphous in the solid state. Both tacticity (i.e., syndio-tactic or isotactic) and geometric isomerism (i.e., trans configuration) favor crystallinity. In general, tactic polymers with their more stereoregular chain structure are more likely to be crystalline than their atactic counterparts. For example, isotactic polypropylene is crystalline, whereas commercial-grade atactic polypropylene is amorphous. Also, cis-pol3nsoprene is amorphous, whereas the more easily packed rans-poly-isoprene is crystalline. In addition to symmetrical chain structures that allow close packing of polymer molecules into crystalline lamellae, specific interactions between chains that favor molecular orientation, favor crystallinity. For example, crystallinity in nylon is enhanced because of... 

The different crystalline forms of several polyamides have been examined by infrared spectroscopy. The bands at 936 and 1140cm have been used to measure the crystalline and amorphous contents, respectively, in nylon-6,6 [309], whereas bands at 1198 and 1181 cm were employed for measuring a and y crystalline content [310]. Fluctuations in crystallinity in nylon-6,6 were related to the ratios 1430/2910 and 930/2910 [311,312]. All even-even nylons show an a-crystal-related peak at 690 cm which appears at 725 cm in odd-odd nylons [313]. In nylon-6, there is a crystallinity band at 1260 cm a-crystalline-sensitive bands at 1028, 960, 950, 930, and 830 cm and 7-crystalline-related bands at 1120, 990, and 970 cm [314—316]. A band at 979 cm has been attributed to the amorphous phase [315]. 

The properties of the nylons are considerably affected by the amount of crystallisation. Whereas in some polymers, e.g. the polyacetals and PCTFE, processing conditions have only a minor influence on crystallinity, in the case of the nylons the crystallinity of a given polymer may vary by as much as 40%. Thus a moulding of nylon 6, slowly cooled and subsequently annealed, may be 50-60% crystalline, while rapidly cooled thin-wall mouldings may be only 10% crystalline. 

An important subdivision within the thermoplastic group of materials is related to whether they have a crystalline (ordered) or an amorphous (random) structure. In practice, of course, it is not possible for a moulded plastic to have a completely crystalline structure due to the complex physical nature of the molecular chains (see Appendix A). Some plastics, such as polyethylene and nylon, can achieve a high degree of crystallinity but they are probably more accurately described as partially crystalline or semi-crystalline. Other plastics such as acrylic and polystyrene are always amorphous. The presence of crystallinity in those plastics capable of crystallising is very dependent on their thermal history and hence on the processing conditions used to produce the moulded article. In turn, the mechanical properties of the moulding are very sensitive to whether or not the plastic possesses crystallinity. 

In a partially crystalline homopolymer, nylon 6, property enhancement has been achieved by blending with a poly(ethylene-co-acrylic acid) or its salt form ionomer [24]. Both additives proved to be effective impact modifiers for nylon 6. For the blends of the acid copolymer with nylon 6, maximum impact performance was obtained by addition of about 10 wt% of the modifier and the impact strength was further enhanced by increasing the acrylic acid content from 3.5 to 6%. However, blends prepared using the salt form ionomer (Sur-lyn 9950-Zn salt) instead of the acid, led to the highest impact strength, with the least reduction in tensile... 

Many aliphatic poly(amides), more commonly known as nylons, exhibit an unusual phase transition below their melting point. First noted by Brill [122], the phenomenon has been studied extensively [128-131]. It is observed for instance in nylon (6,6) at a temperature of about 210°C, when the stable low-temperature triclinic oc phase of the crystalline polymer changes to a pseudo-hexagonal phase. 

Crystallinity. Is one of the key factors influencing properties. You can think of crystallinity in terms of how well a polymer fits in an imaginary pipe, as in Figure 22-6. Linear, straight chains are highly crystalline and fit very well. Bulky groups, coiled chains, and branched chains are not able to line up to fit in the pipe. They are amorphous, the opposite of crystalline. In a spectrum from totally amorphous, to almost totally crystalline, there is methyl methacrylate, polypropylene, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and nylon. 

Examples of crystalline polymers are nylons, cellulose, linear polyesters, and high-density polyethylene. Amorphous polymers are exemplified by poly(methyl methacrylate), polycarbonates, and low-density polyethylene. The student should think about why these structures promote more or less crystallinity in these examples. 

Nylon-4,6 was developed by DSM Engineering Plastics in 1990 and sold under the trade name Stanyl giving a nylon that has a higher heat and chemical resistance for the automotive industry and in electrical applications. It has a of 295°C and can be made more crystalline than nylon-6,6. A number of other nylons, such as the aromatic nylons and aramids, are strong and can operate at high temperatures, and they have good flame-resistant properties. 

Nucleants. Although nylons crystallize quickly, it is often an advantage, particularly for small parts, to accelerate this process to reduce cycle time and increase productivity. Nylon-6, which crystallizes more slowly than nylon-6,6, also benefits from nudeation in unreinforced formulations. Nucleants are generally fine-particle-size solids or materials that crystallize as fine particles before the nylon. The materials, eg, finely dispersed silicas or talc, seed the molten nylon and result in a higher density of small uniformly sized spherulites in nylon-6 the crystalline form is also changed. Nudeation increases tensile strength and stiffness but makes the material more britde. Mold shrinkage is lower for nudeated resins. 

Ergungor describes the application of on-line Raman spectroscopy and neural networks to the simultaneous prediction of temperature and crystallinity of nylon-6 nanocomposites as a function of cooling rate. The authors prefer their neural network approach because they make use of information in the entire spectrum rather than from a few bands as most studies have done.84 Van Wijk etal. of Akzo Nobel obtained a patent on the use of a Raman spectrum of a polymeric fiber to determine dye uptake and other structural or mechanical properties based on previously developed models.85... 

Morphology Some polymers, like PETP, are spun in a nearly amorphous state or show a low degree of crystallinity. In other polymers, such as nylon, the undrawn material is already semi-crystalline. In the latter case the impact of extension energy must be sufficient to (partly) "melt" the folded chain blocks (lamellae) in all cases non-oriented material has to be converted into oriented crystalline material. In order to obtain high-tenacity yarns, the draw ratio must be high enough to transform a fraction of the chains in more or less extended state. 

TABLE 4, 3C NMR Chemical shiftsof methylene in nylon 46 for the crystalline and amorphous phases... 

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