Owing to the fact that heat transfer during the thermally induced phase separation process is limited, a quench rate is inevitably entailed, which leads to the existence of temporal and spatial variations in temperature. Hence, it is of great importance to take into account the nonisothermality during the phase separation process, especially in high viscosity polymer solutions. In this study, the influence of conductive heat transfer on the morphology formation during the thermally induced phase separation process was investigated theoretically in terms of quench depth, boundary conditions, and enthalpy of demixing to elucidate the interaction between temperature and concentration through incorporating the nonlinear Cahn-Hilliard equation and the Fourier heat transfer equation in two dimensions. The Flory-Huggins free energy theory for the thermodynamics of phase separation, slow mode theory, and Rouse law for polymer diffusion without entanglements were taken into account in the model development. The simulation results indicated a strong interaction between heat transfer and phase separation, which impacted the morphology formation significantly. Results confirmed that quench depth had an indispensable impact on phase separation in terms of higher characteristic frequency by increasing the driving force for heat transfer. Applying quench from various boundaries led to a difference in the quench rate due to the high viscosity of the polymer solution. This led to a gradation in pore size and anisotropic morphology formation. The degree and direction of anisotropy depended on quench depth and rate, quench time, heat conduction rate inside the solution, solution viscosity, temperature evolution, and the enthalpy of demixing. It was also verified that the influence of enthalpy of demixing on phase separation could not be neglected as it increased the solution temperature and led to phase separation being accomplished at a higher temperature than the initial quench temperature.
In high‐viscosity polymer solutions and blends, temperature variations during the quench process of the thermally‐induced phase separation (TIPS) influence the dynamics and thermodynamics of phase separation. Hence, this study aims to investigate the impact of temperature variations on the morphology formation during the TIPS process. First, the influence of temporal temperature variations on phase separation is investigated by coupling a transient heat conduction model and the Cahn–Hilliard equation, and the results are compared with the isothermal phase separation process. Next, the morphology formation during phase separation is inspected by applying quench from two opposite sides of the sample to the same and different temperatures through coupling the Fourier heat transfer equation and the Cahn–Hilliard equation. The influence of the enthalpy of demixing on the morphology formation and the competition between the heat and mass transfer is also evaluated. It is confirmed that temporal variations of temperature alone have a significant impact on the morphology formation during the TIPS process. In addition, quenching the system to the same and different temperatures both leads to anisotropic morphology formation, which is affected by the quench rate, quench temperature, solution viscosity, and enthalpy of demixing. Upon applying different quench temperatures from opposite sides, two different types of morphologies and droplet sizes were formed as a result of the difference in the cooling rates between the two sides. Employing the enthalpy of demixing during phase separation induced a shallow quench effect on the deep quench side due to the fact that the heat moved toward the lowest temperature in the system, which led to the formation of a distinctive structure.
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