Mesfin Tsige and Gary S Grest 2005 J. Phys.: Condens. Matter 17 S4119 doi:10.1088/0953-8984/17/49/008
Mesfin Tsige and Gary S Grest
Show affiliationsSolvent evaporation from homopolymer and heteropolymer films along with the interdiffusion of solvent into these films are studied by molecular dynamics simulations. Due to the high viscosity of polymer melts, in many cases polymer films are made by first dissolving the polymer in a low viscosity solvent, spreading the solution on a substrate and subsequently evaporating the solvent. Here we study the last part of this process, namely the evaporation of solvent from a polymer film. As the solvent evaporates, the polymer density at the film/vapour interface is found to increase sharply, creating a polymer density gradient which acts as a barrier for further solvent evaporation. For both homopolymer and heteropolymer films, the rate of solvent evaporation is found to decrease exponentially as a function of time. For multiblock co-polymer films the resulting domain structure is found to be strongly affected by the relative stiffness of the two blocks. The reverse process, namely the interdiffusion of solvent into a polymer film, is also studied. For homopolymer films the weight gain by the film scales as t1/2, which is expected for Fickian diffusion. The diffusivity D(c) determined from the one-dimensional Fick's diffusion equation agrees well with that calculated from the corrected diffusion constant using the Darken equation. Far above the polymer glass transition temperature, D(c) is nearly independent of concentration. However, as the temperature decreases D(c) is found to depend strongly on the state of the polymer and is related to the shape of the solvent concentration profile. Finally, the swelling of a multiblock copolymer film in which the stiffer block is below its glass transition temperature is also studied. While the solvent swells only the softer block of the copolymer, the weight gain by the film remains Fickian.
64.70.F- Liquid–vapor transitions
61.25.H- Macromolecular and polymers solutions; polymer melts
64.70.P- Glass transitions of specific systems
Soft matter, liquids and polymers
Issue 49 (14 December 2005)
Received 18 July 2005, in final form 9 September 2005
Published 25 November 2005
Mesfin Tsige and Gary S Grest 2005 J. Phys.: Condens. Matter 17 S4119
N Papanikolaou et al 2002 J. Phys.: Condens. Matter 14 2799
Kung-Te Chu et al 2005 J. Phys. D: Appl. Phys. 38 4009
Carsten Hutter et al 2006 Europhys. Lett. 74 1088
Marcel Risch et al 2009 J. Phys.: Conf. Ser. 190 012167
Juan Xiong et al 2009 J. Phys. G: Nucl. Part. Phys. 36 125005
Yohan Seo et al 2009 Semicond. Sci. Technol. 24 115016
T Yajima and H Nagahama 2007 J. Phys. A: Math. Theor. 40 2755
M V Ioffe and P A Valinevich 2005 J. Phys. A: Math. Gen. 38 2497
P L Krapivsky 1991 J. Phys. A: Math. Gen. 24 4697