By performing density functional theory-based ab-initio calculations, Raman active phonon modes of novel single-layer two-dimensional (2D) materials and the effect of in-plane biaxial strain on the peak frequencies and corresponding activities of the Raman active modes are calculated.Our findings confirm the Raman spectrum of the unstrained 2D crystals and provide expected variations in the Raman active modes of the crystals under in-plane biaxial strain. The results are summarized as follows; (i) frequencies of the phonon modes soften (harden) under applied tensile (compressive) strains, (ii) the response of the Raman activities to applied strain for the in-plane and out-of-plane vibrational modes have opposite trends, thus, the built-in strains in the materials can be monitored by tracking the relative activities of those modes, (iii) in particular, the A-peak in single-layer Si and Ge disappear under a critical tensile strain, (iv) especially in mono and diatomic single-layers, the shift of the peak frequencies is stronger indication of the strain rather than the change in Raman activities, (v) Raman active modes of single-layer ReX 2 (X=S, Se) are almost irresponsive to the applied strain. Strain-induced modifications in the Raman spectrum of 2D materials in terms of the peak positions and the relative Raman activities of the modes could be a convenient tool for characterization.
Drying and imidization of PMDA−ODA solutions in NMP were investigated by a novel custom designed measurement system that tracks real time weight, thickness, surface temperature, and in-plane and out-of-plane birefringence. At low temperature drying stage, the weight and thickness reductions occurred rapidly as a result of solvent evaporation. All the parameters started leveling off while the out of plane birefringence steadily increased and reached a plateau at longer drying times. When the temperature was increased for imidization reaction, additional weight loss accompanied by temporary reduction of birefringence was observed due to evaporation of bound solvent as solvent molecules decomplexed from the polymer chains and plasticized the film. During the latter stage, out-of-plane birefringence rose rapidly due to increased intrinsic birefringence of the polymer chains due to imidization reaction and orientation of polymer chains with their chain axes preferentially oriented in the film plane. Throughout the whole process the in-plane birefringence remained zero. For the first time, these real time measurements allowed us to quantitatively show the dynamics between chain relaxation due to evaporation of the decomplexed solvent molecules, and orientation development due to decreased chain mobility caused by imidization reaction and increasing T g for the PMDA− ODA/NMP solutions. In addition, the dynamics of this interplay was investigated by varying the processing conditions: initial casting thickness and drying temperature.
This paper describes the design and performance of a new instrument to track temporal changes in physical parameters during the drying behavior of solutions, as well as curing of monomers. This real-time instrument follows in-plane and out-of-plane birefringence, weight, thickness, and surface temperature during the course of solidification of coatings and films through solvent evaporation and thermal or photocuring in a controlled atmosphere. It is specifically designed to simulate behavior of polymer solutions inside an industrial size, continuous roll-to-roll solution casting line and other coating operations where resins are subjected to ultraviolet (UV) curing from monomer precursors. Controlled processing parameters include air speed, temperature, initial cast thickness, and solute concentration, while measured parameters are thickness, weight, film temperature, in-plane and out-of-plane birefringence. In this paper, we illustrate the utility of this instrument with solution cast and dried poly (amide-imide)∕DMAc (Dimethylacetamide) solution, water based black paint, and organo-modified clay∕NMP (N-Methylpyrrolidone) solution. In addition, the physical changes that take place during UV photo polymerization of a monomer are tracked. This instrument is designed to be generic and it can be used for tracking any drying∕swelling∕solidification systems including paper, foodstuffs such as; grains, milk as well as pharmaceutical thin paste and slurries.
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