Formation of Spherulites

The formation of the microstructure involves the folding of linear segments of polymer chains in an orderly manner to form a crystalline lamellae, which tends to organize into a spherulite structure. The SCB hinder the formation of spherulite. However, the volume of spherulite/axialites increases if the branched segments participate in their formation [59]. Heterogeneity due to MW and SCB leads to segregation of PE molecules on solidification [59-65], The low MW species are accumulated in the peripheral parts of the spherulite/axialites [63]. The low-MW segregated material is brittle due to a low concentration of interlamellar tie chains [65] and... 

We have already mentioned that depending on composition, semicrystalline triblock copolymers can show some conflict between microphase separation and superstructure formation. In fact, one of the controversial aspects is the question whether block copolymers can or cannot exhibit spherulites. This is a relevant question because spherulitic structures greatly affect the ultimate mechanical properties, and the boundaries between adjacent spherulites are often weak points in mechanical performance. Kim et al. [125] studied the competition between crystallization within microphase-separated regions and reorganization into supermolecu-lar spherulites in semicrystalline PS-b-PB-b-PCL triblock copolymers. These authors found that the formation of spherulites is strongly affected by the thickness of the specimen in such a way that thin films crystallize into... 

Ueda et al. [26] recently investigated a flow-oriented PE-fr-aPP diblock copolymer with Mw = 113 000 (Mn/Mw = 1.1) and a PE volume fraction of 0.48. This diblock copolymer is in the strong segregation regime (i.e., estimated xN = 10.5 and Todt = 290 °C) and has a lamellar morphology in the melt. They found a breakout phenomenon with the formation of spherulites in an intermediate crystallization temperature range 95 < Tc < 101 °C. At crystallization temperatures above 101 °C or below 95 °C spherulites were not formed and the crystallization was confined within the lamellar MD. Ueda et al. report that lamellar MD and spherulites do not co-exist when the material crystallizes from the melt which is separated in lamellar MDs. In other words, in this particular case, breakout or confined crystallization within lamellar MDs depends on the crystallization conditions. 

For linear PE, the initial structure formed is a single crystal with folded chain lamellae. These quickly lead to the formation of sheaflike structures called axialites or hedrites. As growth proceeds, the lamellae develop on either side of a central reference point. They continue to fan out, occupying increasing volume sections through the formation of additional lamellae at appropriate branch points. The result is the formation of spherulites as pictured in Figures 2.15 and 2.16. 

Applications. Optical microscopy finds several important applications in filled systems, including observation of crystallization and formation of spherulites and phase morphology of polymer blends. " In the first case, important information can be obtained on the effect of filler on matrix crystallization. In polymer blends, fillers may affect phase separation or may be preferentially located in one phase, affecting many physical properties such as conductivity (both thermal and electrical) and mechanical performance. 

Testing procedure. Testing of thermal properties is a fairly standard procedure which is not discussed here. DSC was used for the studies on the effect of cooling rate on formation of spherulites in the presence of fillers. In order to assure the repeatability of conditions of the experiment, the instrument was calibrated with indium and tin standards. The TGA/DSC instrument was coupled with a mass... 

Another characteristic feature of polyethyleneterephthalate is almost plane configuration of chains and presence of two centres of symmetiy on each repeat unit [188], These two features cause the ability of PETP to crystallization [189], Crystallization of PETP flows with formation of spherulite structure leading to polymer turbidity. 

Abstract. Structural properties of rubrene thin films on cleaved mica (001) surfaces were investigated by optical microscopy and x-ray diffraction. Optical microscopy shows, that the crystallization of rubrene results in formation of spherulites. X-ray specular diffraction reveals polycrystalline and polymorphic nature of rubrene. The pole figure measurements of films prepared at low deposition rates reveal orthorhombic structure and indicate fiber textures with crystallographic planes (121), (131) and (141) preferentially oriented parallel to the substrate surface. High deposition rate thin films in addition show polymorphism, corroborating the existence of the orthorhombic and the triclinic phase. 

L.S. Pinchuk and A.S. Mikhnevich. On the substrate effect upon formation of spherulitic thermoplastic structure from melt. Proc. Belarus AS, 1976, Vol. 

During the course of the pyrolysis of a petroleum-derived residue (pyrolysis tar, cat-cracker residue) or a filtered coal tar pitch it is possible to observe, under the polarisation microscope and at a certain temperature, the formation of anisotropic spherules, which grow as the reaction time lengthens and the temperature increases, coalesce and, at around 500 to 600 °C, are transformed into a semi-coke phase with marked anisotropy. Figure 13.2 shows photomicrographs of a filtered coal tar pitch pyrolyzed at 400 °C with the formation of spherulitic mesophases after reaction times of 2, 6,10 and 16 hours. 

In PEEK/CaC03 composite, nucleation started homogeneously throughout the matrix, the particles were observed to act not as nucleation sites, evidenced by a significant increase in time to reach the exothermal peak. The PEEK molecules in the vicinity of the finely dispersed CaC03 particles are hindered in their mobihty and cannot participate readily in the formation of spherulites. ... 

Recently the statistical approach was developed [5] for the description of the kinetics of conversion of melt to spherulites and the kinetics of formation of spherulitic pattern during both isothermal and nonisothermal crystallizations. The final spherulitic pattern can also be described. The rates of formation of spherulitic interiors and boundaries (boundary lines, surfaces and points) as well as the their final amounts could be predicted if spherulite growth and nucleation rates are known. Applied to iPP crystallized during cooling with various rates, the approach allowed for the predictions of tendencies in the kinetics of formation of spherulitic structure and its final form. 

Fig. 1.2 Polarized light micrograph of this polyoxymethylene film cooled from melt shows recrystallization and formation of spherulites. The shape of the growing, birefringent spherulites is round.

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