Issue
Korean Journal of Chemical Engineering,
Vol.19, No.1, 153-158, 2002
The Miscibility and Phase Behavior of Polyethylene with Poly(dimethylsiloxane) in Near-Critical Pentane
Miscibility and phase behavior of solutions of polyethylene (PE) and poly(dimethylsiloxane) (PDMS) mixtures in near-critical n-pentane have been investigated in a special variable-volume view-cell equipped with a computerized data acquisition system. This is a study on dissolving mutually incompatible polymers in a common solvent at high pressures. The fluid-fluid and fluid-solid demixing pressures of the solutions were determined for different polymer concentrations (5% PE, 5% PE+1% PDMS, 5% PE+2% PDMS and 5% PE+5% PDMS). In the PE+n-pentane solutions, the system shows LCST (lower critical solution temperature) type behavior and the fluid-fluid demixing pressures increase with increasing temperature. The PE+PDMS+n-pentane systems, however, show UCST (upper critical solution temperature) type behavior and the fluid-fluid demixing pressures decrease with increasing temperature. Even with small addition of PDMS to PE, the demixing pressures show dramatic increases compared to the demixing pressures of PE alone. At high PDMS concentrations (5% PDMS), complete miscibility could not be achieved at pressures up to 70 MPa. The fluid-solid boundary that is associated with the melting or crystallization of PE was also studied as a function of cooling and heating rates. It is shown that these temperatures tend to approach the same value in the limit of very low heating and cooling rates.
[References]
  1. Bayraktar Z, Kiran E, J. Appl. Polym. Sci., 75(11), 1397, 2000
  2. Bayraktar Z, Kiran E, "Polymer Blending by Pressure-Induced Swelling,Impregnation and Phase Separation in Supercritical Fluids. Gradient Blending and Phase Localization of Poly(dimethylsiloxane) in Polystyrene and Polyethylene," Proc. 2nd Int. Meeting on High Pressure Chemical Engineering, Hamburg, Germany, March 7-9, 2001
  3. Chalykh AY, Avdeyev NN, Polym. Sci. USSR., 27, 2769, 1985
  4. Huglin MB, Idris IM, Polymer, 24, 1434, 1983
  5. Huglin MB, Idris IM, Eur. Polym. J., 21, 9, 1985
  6. Kiran E, "Polymer Formation, Modification and Processing in or with Supercritical Fluids," Supercritical Fluids, Kiran, E. and Levelt Sengers, J.M.H., eds., Kluwer Academic Publishers, Dordrecht, Netherlands, 541, 1994
  7. Kiran E, "Polymer Miscibility and Kinetics of Pressure-Induced Phase Separation in Near-Critical and Supercritical Fluids," Supercritical Fluids Fundamentals and Applications, Kiran, E., Debenedetti, P.G. and Peters, C.J., eds., Kluwer Academic Publishers, Dordrecht, Netherlands, 167, 2000
  8. Kiran E, "Miscibility of Mutually Incompatible Polymers in Near-Critical Fluids: Solution Blending," Proc. 10th Symposium on Supercritical Fluid Chromatography and Extraction and Processing,Myrtle Beach, South Carolina, U.S.A., August 19-22, 2001
  9. Kiran E, Liu K, Bayraktar Z, "Polymer Solutions at High Pressures: Pressure-Induced Miscibility and Phase Separation in Near-Critical and Supercritical Fluids," Computational Studies, Nanotechnology and Solution Thermodynamics of Polymer Systems, Dadmun, M.D. et al., eds., Kluwer Academic/ Plenum Published, New York, 2000
  10. Kiran E, Zhuang W, "Miscibility and Phase Separation of Polymers in Near-and Supercritical Fluids," Supercritical Fluids-Extraction and Pollution Prevention, Abraham, M.A. and Sunol, A.K., eds., ACS Symposium Series No 670, American Chemical Society, Washington, D.C., 2, 1997
  11. Kiran E, Zhuang W, Sen YL, J. Appl. Polym. Sci., 47, 895, 1993