• Volume/Page
  • Keyword
  • DOI
  • Citation
  • Advanced
   
 
 
 

J. Rheol. 46, 145 (2002); http://dx.doi.org/10.1122/1.1427912 (23 pages)

Slip at polymer–polymer interfaces: Rheological measurements on coextruded multilayers

Rui Zhao and Christopher W. Macosko

Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Avenue SE, Minneapolis, Minnesota 55455

Full Text: Read Online (HTML) | Download PDF FREE | View Cart
Polypropylene (PP) and polystyrene (PS), with closely matched viscosity, were coextruded into 8, 32, and 64 alternating layers. The apparent steady shear viscosity of these multilayer samples was measured with an in-line slit rheometer and with a parallel-plate rheometer. In both cases the apparent viscosity decreased with the number of layers providing strong evidence for interfacial slip. The velocity difference across the interface (interfacial slip velocity) versus shear stress, ΔVI(τ) was calculated from the apparent viscosity measurements. ΔVI(τ) showed sigmoidal behavior: a region of very low slip (< 10−3μm) at low shear stress, a strongly increasing region at τ > 103 Pa followed by a linear region ΔVI = τ/β. These data could be fit with a modified Ellis model. The same function fit the different number of layers and both slit and parallel-plate data indicating ΔVI(τ) is a material property of the PP/PS pair. Slip was also observed in PS/PMMA (polymethyl methacrylate) and PP/aPA (amorphous nylon) pairs. Addition of a premade P(S-b-EE) diblock copolymer to the PP/PS pair was able to suppress the interfacial slip but only after enough time for sufficient block copolymers to diffuse to the interfaces. The in situ formed graft copolymer of maleated PP with aPA at the interface of the PP/aPA pair directly suppressed the slip. Our results are in qualitative agreement with the theory of Furukawa (1989) and de Gennes (1992), which predicts fewer chain entanglements near the interface between two immiscible polymers, and thus a narrow region (∼ interfacial width) with lower viscosity. This lower viscosity is the cause of apparent interfacial slip. Goveas and Fredrickson (1998) extended these ideas to calculate the slip in a symmetric bilayer where both bulk and interface are Newtonian. Their results are in qualitative agreement with our observation but predict a stronger slip. Our results also indicate that the anomalously low viscosity reported by a number of researchers for immiscible polymer blends is due to interfacial slip. Blends of PP and PS show similar negative viscosity deviations to those reported but only at τ > 2000 Pa. No negative deviations were found for linear viscoelastic (low-stress) measurements. © 2002 The Society of Rheology.

© 2002 The Society of Rheology

KEYWORDS and PACS

PACS

  • 83.80.Sg

    Polymer melts

  • 83.50.Lh

    Slip boundary effects (interfacial and free surface flows)

  • 66.20.-d

    Viscosity of liquids; diffusive momentum transport

  • 81.10.Fq

    Growth from melts; zone melting and refining

  • 47.45.Gx

    Slip flows and accommodation

  • 47.50.-d

    Non-Newtonian fluid flows

  • 61.25.H-

    Macromolecular and polymers solutions; polymer melts

  • 83.60.Bc

    Linear viscoelasticity

  • 83.60.Fg

    Shear rate dependent viscosity

  • 83.80.Tc

    Polymer blends

  • 83.80.Uv

    Block copolymers

PUBLICATION DATA

ISSN

0148-6055 (print)  

ARTICLE DATA

History
Received 10 May 01
Revised 10 Oct 01

  1. Alle, N. and J. Lyngaae -Jorgensen, "Polypropylene and polyethylene blends. I. Flow behavior in capillaries," Rheol. Acta 19, 94–103 (1980). [Inspec] [ISI]
  2. Bousmina, M., J. F. Palierne, and L. A. Utracki, "Modeling of structured polyblend flow in a laminar shear field," Polym. Eng. Sci. 39, 1049–1059 (1999). [Inspec] [ISI]
  3. Brochard-Wyart, F., P. G. de Gennes, and S. Troian, "Slippage at the interface between two slightly incompatible polymers," C. R. Acad. Sci., Ser. II: Mec., Phys., Chim., Sci. Terre Univers 310, 1169–1173 (1990). [Inspec]
  4. Chan, C. M. and J. Feng, "Mechanisms for viscosity reduction of polymer blends: Blends of fluoroelastomer and high-density polyethylene," J. Rheol. 41, 319–333 (1997)JORHD2000041000002000319000001.
  5. Cohen, A. and J. R. Schroeder, "Morphological analysis of the viscosity anomaly for PP/PS blends," J. Rheol. 34, 685–704 (1990)JORHD2000034000005000685000001.
  6. Cole, P. J. and C. W. Masoko, "Polymer–polymer adhesion in melt processed layered structures," J. Plast. Film Sheeting 16, 213–222 (2000). [ISI]
  7. Danesi, S. and R. S. Porter, "Blends of isotactic polypropylene and ethylene–propylene rubbers. Rheology, morphology and mechanics," Polymer 19, 448–457 (1978). [ISI]
  8. de Gennes, P. G., "Viscometric flows of tangled polymers," C. R. Acad. Sci. Paris, Ser. B 288, 219–220 (1979). [Inspec]
  9. de Gennes, P. G., "Mechanical properties of polymer interfaces," in Physics of Polymer Surfaces and Interfaces, edited by I. C. Sanchez (Butterworth-Heinemann, MA, 1992), pp. 55–71.
  10. Denn, M. M., "Extrusion instabilities and wall slip," Annu. Rev. Fluid Mech. 33, 265–287 (2001).
  11. Doi, M. and T. Ohta, "Dynamics and rheology of complex interfaces. I," J. Chem. Phys. 15, 1242–1248 (1991).
  12. door Sluijters, R., "V. Het principe van de multifluxmenger," Chem. Tech. (Leipzig) 3, 33–36 (1965).
  13. Fetters, L. J., D. J. Lohse, and W. W. Graessley, "Chain dimensions and entanglement spacings in dense macromolecular systems," J. Polym. Sci., Part B: Polym. Phys. 37, 1023–1033 (1999).
  14. Furukawa, H., "Sliding along the interface of strongly segregated polymer melts," Phys. Rev. A 40, 6403–6406 (1989). [MEDLINE]
  15. Goveas, J. L. and P. G. Fredrickson, "Apparent slip at a polymer–polymer interfaces," Eur. Phys. J. B 2, 79–92 (1998). [Inspec] [ISI]
  16. Grulke, E. A., "Solubility parameter values," in Polymer Handbook 3, VII ed., edited by J. Brandrup and E. H. Immergut (Wiley, New York, 1989), pp. 519–559.
  17. Han, C. D. and T. C. Yu, "Rheological properties of molten polymers. II. Two-phase systems," J. Appl. Polym. Sci. 15, 1163–1180 (1971). [ISI]
  18. Han, C. D. and T. C. Yu, "Rheological behavior of two-phase polymer melts," Polym. Eng. Sci. 12, 81–90 (1972). [ISI]
  19. Heitmiller, R. F., R. Z. Naar, and H. H. Zabusky, "Effect of homogeneity on viscosity in capillary extrusion of polyethylene," J. Appl. Polym. Sci. 8, 873–880 (1964).
  20. Helfand, E. and Y. Tagami, "Theory of the interface between immiscible polymers," J. Chem. Phys. 57, 1812–1813 (1972)JCPSA6000057000004001812000001. [ISI]
  21. Johnson, J. E., "Coextrusion," Plast. Technol. 22, 45–49 (1976).
  22. Jones, T. D., "Modification of polypropylene through blending," Ph.D. thesis, University of Minnesota (2000).
  23. Kapuscinski, M. and H. P. Schreiber, "Effects of dispersion on flow and mechanical properties of polymer blends," Polym. Eng. Sci. 19, 900–906 (1979). [ISI]
  24. Kinning, D. J., E. L. Thomas, and L. J. Fetters, "Morphological studies of micelle formation in block copolymer/homopolymer blends," J. Chem. Phys. 90, 5806–5825 (1989)JCPSA6000090000010005806000001. [ISI]
  25. Levitt, L. and C. W. Macosko, "Shearing of polymer drops with interface modification," Macromolecules 32, 6270–6277 (1999).
  26. Lin, C. C., "A mathematical model for viscosity in capillary extrusion of two-component polyblends," Polym. J. (Tokyo) 11, 185–192 (1979). [ISI]
  27. Lipatov, Y. S., V. F. Shumsky, A. N. Gorbatenko, Y. N. Panov, and L. S. Bolotnikova, "Viscoelastic properties of polystyrene–polycarbonate blends in melt," J. Appl. Polym. Sci. 26, 499–508 (1981). [ISI]
  28. Lyngaae-Jorgensen, J., L. D. Thomsen, K. Rasmussen, K. Sondergaard, and F. E. Andersen, "On the influence of interfacial slip on melt flow properties of polymer blends," Int. Polym. Process. 2, 123–130 (1988).
  29. Macosko, C. W., Rheology—Principles, Measurements, and Applications (Wiley, New York, 1994).
  30. Macosko, C. W., "Morphology development and control in immiscible polymer blends," Macromol. Symp. 149, 171–184 (2000). [ISI]
  31. Macosko, C. W., P. Guégan, A. K. Khandpur, A. Nakayama, P. Marechal, and T. Inoue, "Compatibilizers for melt blending: Premade block copolymers," Macromolecules 29, 5590–5598 (1996). [ISI]
  32. Matsuhisa, S. and R. B. Bird, "Analytical and numerical solutions for laminar flow of the non-Newtonian Ellis fluid," AIChE J. 11, 588–595 (1965). [ISI]
  33. Migler, K. B., C. Lavallé, M. P. Dillon, S. S. Woods, and C. L. Gettinger, "Visualizing the elimination of sharkskin through fluropolymer additives: Coating and polymer–polymer slippage," J. Rheol. 45, 565–581 (2001)JORHD2000045000002000565000001. [ISI]
  34. Miroshnikov, Y. P. and E. N. Andreeva, "Flow of polypropylene–polystyrene blends having coaxial phase structure," Vysokomol. Soedin., Ser. A 29, 579–582 (1987). [Inspec] [ISI]
  35. Orr, C. A., A. Adedeji, A. Hirao, F. S. Bates, and C. W. Macosko, "Flow-induced reactive self-assembly," Macromolecules 30, 1243–1246 (1997). [ISI]
  36. Orr, C. A., J. J. Cernohous, P. Guégan, A. Hirao, H. K. Jeon, and C. W. Macosko, "Homogeneous reactive coupling of terminally functional polymers," Polymer 42, 8171–8178 (2001). [ISI]
  37. Palierne, J. F., "Linear rheology of viscoelastic emulsions with interfacial tension," Rheol. Acta 29, 204–214 (1990). [Inspec] [ISI]
  38. Press, W. H., S. A. Teukolsky, W. T. Vetterling, and B. P. Flannery, Numerical Recipes in Fortran: The Art of Scientific Computing (Cambridge University Press, New York, 1992).
  39. Riemann, R. E., H. J. Cantow, and C. Friedrich, "Interpretation of a new interface-governed relaxation process in compatibilized polymer blends," Macromolecules 30, 5476–5484 (1997). [ISI]
  40. Saito, T. and C. W. Macosko, "Interfacial reaction versus area generation rate via extensional rheometry," Annu. Tech. Conf.-Soc. Plast. Eng. 56, 967–971 (1998).
  41. Schrenk, W. J. and T. Alfrey, Jr., "Some physical properties of multilayered films," Polym. Eng. Sci. 9, 393–399 (1969). [ISI]
  42. Schrenk, W. J. and T. Alfrey, Jr., "Coextruded multilayer polymer films and sheets," in Polymer Blends, edited by D. R. Paul and S. Newman (Academic Press, New York, 1978), Vol. 2, pp. 129–165.
  43. Shih, C. K., "Rheological properties of incompatible blends of two elastomers," Polym. Eng. Sci. 16, 742–746 (1976). [ISI]
  44. Silliman, W. J. and L. E. Scriven, "Separating Flow Near a Static Contact Line: Slip at a Wall and Shape of a Free Surface," J. Comput. Phys. 34, 287–313 (1980). [Inspec] [ISI]
  45. Utracki, L. A., "Melt flow of polymer blends," Polym. Eng. Sci. 23, 602–609 (1983). [Inspec] [ISI]
  46. Utracki, L. A. and M. R. Kamal, "Melt rheology of polymer blends," Polym. Eng. Sci. 22, 96–114 (1982). [Inspec] [ISI]
  47. van der Hoeven, J. C., R. Wimberger-Friedl, and H. E. H. Meijer, "Homogeneity of multilayers produced with a static mixer," Polym. Eng. Sci. 41, 32–42 (2001). [ISI]
  48. Wang, S. Q., "Molecular transitions and dynamics at polymer/wall interfaces: Origins of flow instabilities and wall slip," Adv. Polym. Sci. 138, 227–275 (1999). [ISI]
  49. Weimann, P. A., T. D. Jones, M. A. Hillmyer, F. S. Bates, J. D. Londono, Y. Melnichenko, G. D. Wignall, and K. Almdal, "Phase behavior of isotactic polypropylene-poly(ethylene/ethylethylene) random copolymer blends," Macromolecules 30, 3650–3657 (1997). [ISI]
  50. Wu, S., Polymer Interface and Adhesion (Marcel Dekker, New York, Vol. 1982).
  51. Yokoyama, H., E. J. Kramer, D. A. Hajduk, and F. S. Bates, "Diffusion in mixtures of asymmetric diblock copolymers with homopolymers," Macromolecules 32, 3353–3359 (1999). [ISI]
  52. Zhao, J., L. Mascia, and V. Nassehi, "Simulation of the rheological behavior of polymer blends by finite element analysis," Adv. Polym. Technol. 16, 209–226 (1997). [Inspec] [ISI]
  53. Zhao, R., "Multilayer coextrusion reveals interfacial dynamics in polymer blending," Ph.D. thesis, University of Minnesota (2001).


Close
   

close