Effect of thermal history during drying and curing process on the chain orientation of rod-shaped polyimide

- Chain orientation of polyimide film made by different thermal history was investigated.
- Residual solvent content and imidization degree were measured during the process.
- The process path was proposed to explain the variation in chain orientation.
- Chain orientation most critically influenced thermal expansion coefficient of the film.

Chain orientation in polyimide (PI) film is influenced by the thermal history during drying and curing process. The amount of residual solvent and the degree of imidization, among other factors, play a major role in determining the chain orientation during the process. In the present study, poly(amic acid), the precursor of PI, coated on the glass substrate was imidized to PI through different drying and curing protocols. On the way of complete imidization, the residual solvent concentration and the degree of imidization were characterized using confocal Raman spectroscopy. The poly(amic acid) began to imidize quickly while retaining more solvent in the film as the initial drying temperature increased. The degree of in-plane chain orientation in fully imidized PI film made by different process protocols was compared using polarized Raman spectroscopy. The fully imidized PI showed the lowest degree of in-plane chain orientation when it was processed by the protocol with the highest drying temperature. The difference in the degree of in-plane chain orientation among different PI films significantly influenced the in-plane thermal expansion coefficient, while no significant change in crystallinity or glass transition temperature was observed.