As-cast and slowly crystallized films of conjugated polymers can contain (partially) ordered and less ordered (amorphous) regions with structural defects. Crystallization allows to generate chains with highly planarized backbones, embedded in structures exhibiting long-range order. In the present study, we used spatially resolved optical spectroscopy to quantify differences in the degree of order of a bulky substituted poly(3-(2,5-dioctylphenyl)thiophene) (PDOPT). In particular, we compared absorption and photoluminescence (PL) measurements from large spherulitic crystals, and the same region rapidly recrystallized after melting, which allowed to identify characteristic features of ordered and less ordered regions. In addition, on the basis of temperature-dependent absorbance and PL measurements, we followed in situ melting and recrystallization processes, i.e., transitions between ordered and disordered phases. A multipeak analysis of absorption and PL spectra based on a modified Franck−Condon progression showed changes in for example the relative intensities of each peak, the excitonic bandwidth, and the vibronic energy as a function of temperature. Most importantly, at the phase transition temperature, a clear change in the positions of the peaks (i.e., their wavelengths, corresponding to the energy of the emitted photons) was detected. In particular, the relative absorption and PL intensities depended sensitively on the extent of order within PDOPT samples. Furthermore, on the basis of a comparison with calorimetric measurements, we have confirmed correlations between changes in the relative absorbance and PL intensities with variations in order/disorder occurring during melting and recrystallization.

We investigated non-isothermal and isothermal crystallization of spin-coated poly(3-hexylthiophene) thin films prepared from the melt by in-situ ultraviolet-visible absorption spectroscopy. Analyzing the absorption spectra according to the Franck-Condon principle allowed for a quantitative assessment of the degree of crystallinity as well as the quality of order within crystalline regions of the films. Measured at room temperature, we observed a similar crystallinity for all differently crystallized films. The highest quality of order, however, was found for the P3HT film cooled slowly from the melt. These results were in full agreement with the results obtained by X-ray diffraction and calorimetry measurements. Consistently, in spite of similar crystallinities, atomic force microscopy images did not show a well-defined structure of ordered domains of preferentially aligned lamellae for the films rapidly cooled from the melt. In addition, heating the P3HT films in a specific range of temperature showed no change in crystallinity in spite of a continuous loss of order quality. Our results revealed that crystallinity and crystalline quality could behave differently while processing a semicrystalline polymer.

S12 -S15 5.13 C chemical shift increments S16 6.Assignment of 1 H and 13 C chemical shifts to PDOPT end groups and regio-irregularities I -VII S16 -S17 7.Additional 13 C NMR and HSQC spectra of PDOPT synthesized from DAP and KCTP S18 -S20 8.References S20

Carbon nanomaterials have recently attracted wide scientific applications due to their tunable properties. These novel materials act as best fillers that can provide substantial benefits due to their high strength, thermal conductivity, and electrical conductivities. With their huge applications as bulk materials, when implemented in polymer matrix as fillers, they give rise to new promising materials with which their properties can be tuned to suit a particular application. Besides the development of these new nanocomposite materials, there exist some challenges which must be fully surpassed to explore the potentiality of application of carbon-based nanocomposites. Reduced graphene oxide is one of the carbon derivatives which has attracted the current advancement in technology, and recently, it found its new applications in super capacitors used in electronic industries. The limiting factor for its exploration is the affordability. New and affordable sources of these graphene-based nanomaterial have to be devised, for fully realization of their potential applications. In this study, reduced graphene oxide and the bio-polymer chitosan were extracted from the locally available bio waste materials. Nanocomposites were prepared at 50% rGO: chitosan ratio. The films were then prepared by spin coating method. Prepared films were subjected to morphological analysis. From the results, it was observed that rGO induced chitosan crystallization, which led to formation of dendritic structures. Cellulose nanocrystals have thus displayed temperature dependent positive uniaxial birefringence