Crystalline polymers structure-property

Interestingly, the amorphous regions within the spherulite confer some flexibility onto the material while crystalline platelets give the material strength, just as in the case with largely amorphous materials. This theme of amorphous flexibility and crystalline strength (and brittleness) is a central idea in polymer structure-property relationships. 

R.J. Samuels, Structured polymer properties the identification, interpretation, and apphcation of crystalline polymer structure, (New York John Wiley 1974)... 

R. J. Samuels, Structured Polymer Properties The Identification, Interpretation, and Application of Crystalline Polymer Structure, John Wiley Sons, Inc., New York, 1974. 

Fig. 11.1 Correlations between structure and morphology (dependent on crystallization conditions and processing) and the mechanical properties of semi-crystalline polymers. These properties depend on the chain architecture that in turn depends on the polymerization set-up...

The mechanical properties of commercial poly(lactic acid) (PLA) can be varied, ranging from soft, elastic materials to stiff, high-strength materials, according to different parameters, such as crystallinity, polymer structure, molecular weight, material formulation (blends, plasticizers, composites, etc.) and orientation.Table 5.1 summarizes some of the mechanical properties of PLA developed by NatureWorks LLC. 

A. Peterlin, Microfibrillar Structure, Radical Formation, and Fracture of Highly Drawn Crystalline Polymers - Structure and Properties of Polymer Fibers, Ed. by R. W. Lenz and R. S. Stein (Polymer Sci. Technol. X) 9 Plenum Press, New York-London... 

The adoption of altered polymer chain-polymer chain morphologies for polymer-montmorillonite nanocomposites, particularly for crystalline polymers, indicates the significance of the energetic compromises associated with nanocomposite construction. The success of the preparation of nylon 6 nanocomposites in relation to the difficulties associated with the preparation of nylon 6,6 nanocomposites illustrates the sensitivity of the preparation of polymer nanocomposites to the fundamental polymer structure-property relationships. 

X-ray Diffraction (XRD) is a powerful technique used to uniquely identify the crystalline phases present in materials and to measure the structural properties (strain state, grain size, epitaxy, phase composition, preferred orientation, and defect structure) of these phases. XRD is also used to determine the thickness of thin films and multilayers, and atomic arrangements in amorphous materials (including polymers) and at inter ces. 

Figure 3.6). This theory known as the fringed mieelle theory or fringed crystallite theory helped to explain many properties of crystalline polymers but it was difficult to explain the formation of certain larger structures such as spherulites which could possess a diameter as large as 0.1 mm. 

In the case of commercial crystalline polymers wider differences are to be noted. Many polyethylenes have a yield strength below 20001bf/in (14 MPa) whilst the nylons may have a value of 12 000 Ibf/in (83 MPa). In these polymers the intermolecular attraction, the molecular weight and the type and amount of crystalline structure all influence the mechanical properties. 

Structurally the difference between PEN and PET is in the double (naphthenic) ring of the former compared to the single (benzene) ring of the latter. This leads to a stiffer chain so that both and are higher for PEN than for PET (Tg is 124°C for PEN, 75°C for PET is 270-273°C for PEN and 256-265°C for PET). Although PEN crystallises at a slower rate than PET, crystallization is (as with PET) enhanced by biaxial orientation and the barrier properties are much superior to PET with up to a fivefold enhancement in some cases. (As with many crystalline polymers the maximum rate of crystallisation occurs at temperatures about midway between Tg and in the case of both PEN and PET). At the present time PEN is significantly more expensive than PET partly due to the economies of scale and partly due to the fact that the transesterification route used with PEN is inherently more expensive than the direct acid routes now used with PET. This has led to the availability of copolymers and of blends which have intermediate properties. 

Many engineering thermoplastics (e.g., polysulfone, polycarbonate, etc.) have limited utility in applications that require exposure to chemical environments. Environmental stress cracking [13] occurs when a stressed polymer is exposed to solvents. Poly(aryl ether phenylquin-oxalines) [27] and poly(aryl ether benzoxazoles) [60] show poor resistance to environmental stress cracking in the presence of acetone, chloroform, etc. This is expected because these structures are amorphous, and there is no crystallinity or liquid crystalline type structure to give solvent resistance. Thus, these materials may have limited utility in processes or applications that require multiple solvent coatings or exposures, whereas acetylene terminated polyaryl ethers [13] exhibit excellent processability, high adhesive properties, and good resistance to hydraulic fluid. 

MW and MWD are very significant parameters in determining the end use performance of polymers. However, difficulty arises in ascertaining the structural properties relationship, especially for the crystalline polymers, due to the interdependent variables, i.e., crystallinity, orientation, crystal structure, processing conditions, etc., which are influenced by MW and MWD of the material. The presence of chain branches and their distribution in PE cause further complications in establishing this correlation. 

Another natural polymer that needs a fresh look into its structure and properties is bitumen [123], also called asphaltines, that are used in highway construction. Although a petroleum by-product, it is a naturally existing polymer. It primarily consists of polynuclear aromatic and cyclocaliphatic ring systems and possesses a lamellar-type structure. It is a potential material that requires more study, and high-performance materials such as liquid crystalline polymer (LCP) could be made from it. 

The Emerman model described in the previous section is hardly applicable to the carbon black-filled CCM as the black particles have sizes of hundreds angstrom and such a composite, compared with the molding channel size, may be considered as a homogeneous viscous fluid. Therefore, the polymer structure, crystallinity and orientation play an important role for such small particles. The above-given example of manufacture of the CCM demonstrates the importance of these factors being considered during processing of a composite material to and article with the desired electrical properties. 

Due to dieir compact, branched structure and to die resulting lack of chain entanglement, dendritic polymers exhibit much lower melt and solution viscosity dian their lineal" counterparts. Low a-values in die Mark-Houwink-Sakurada intrinsic viscosity-molar mass equation have been reported for hyperbranched polyesters.198 199 Dendrimers do not obey diis equation, a maximum being observed in die corresponding log-log viscosity-molar mass curves.200 The lack of chain entanglements, which are responsible for most of the polymer mechanical properties, also explains why hyperbranched polymers cannot be used as diermoplastics for structural applications. Aldiough some crystalline or liquid... 

Aliphatic polyesters based on monomers other than a-hydroxyalkanoic acids have also been developed and evaluated as drug delivery matrices. These include the polyhydroxybutyrate and polyhydroxy valerate homo- and copolymers developed by Imperial Chemical Industries (ICI) from a fermentation process and the polycaprolactones extensively studied by Pitt and Schindler (14,15). The homopolymers in these series of aliphatic polyesters are hydrophobic and crystalline in structure. Because of these properties, these polyesters normally have long degradation times in vivo of 1-2 years. However, the use of copolymers and in the case of polycaprolactone even polymer blends have led to materials with useful degradation times as a result of changes in the crystallinity and hydrophobicity of these polymers. An even larger family of polymers based upon hydroxyaliphatic acids has recently been prepared by bacteria fermentation processes, and it is anticipated that some of these materials may be evaluated for drug delivery as soon as they become commercially available. 

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