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Polymer Thermodynamics pp 179–269Cite as

Interfacial Tension in Binary Polymer Blends and the Effects of Copolymers as Emulsifying Agents

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Part of the book series: Advances in Polymer Science ((POLYMER,volume 238))

Abstract

The structure and the thermodynamic state of polymeric interfaces are important features in many materials of technological interest. This is especially true for multiconstituent systems such as blends of immiscible polymers, where the interface structure can affect greatly their morphology and, thus, their mechanical properties. In this article, we first present a review of the experimental and theoretical investigations of the interfacial tension in phase-separated homopolymer blends. We emphasize the effects of temperature and molecular weight on the behavior: interfacial tension γ decreases with increasing temperature (for polymer systems exhibiting upper critical solution temperature behavior) with a temperature coefficient of the order of 10–2 dyn/(cm °C), whereas it increases with increasing molecular weight. The increase follows a \(\gamma = \gamma _\infty \left( {1 - k_{\operatorname{int} } M_{\text{n}}^{ - z} } \right)\) dependence (with z ≈ 1 for high molecular weights), where γ ∞ is the limiting interfacial tension at infinite molecular weight and M n the number average molecular weight. Suitably chosen block or graft copolymers are widely used in blends of immiscible polymers as compatibilizers for controlling the morphology (phase structure) and the interfacial adhesion between the phases. The compatabilitizing effect is due to their interfacial activity, i.e., to their affinity to selectively segregate to the interface between the phase-separated homopolymers, thus reducing the interfacial tension between the two macrophases. The experimental and theoretical works in this area are reviewed herein. The effects of concentration, molecular weight, composition, and macromolecular architecture of the copolymeric additives are discussed. An issue that can influence the efficient utilization of a copolymeric additive as an emulsifier is the possibility of micelle formation within the homopolymer matrices when the additive is mixed with one of the components. These micelles will compete with the interfacial region for copolymer chains. A second issue relates to the possible trapping of copolymer chains at the interface, which can lead to stationary states of partial equilibrium. The in-situ formation of copolymers by the interfacial reaction of functionalized homopolymers is also discussed.

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Notes

  1. 1.

    It is noted that Noolandi [288] objects to the use of (107) and (112) because he claims that the main contribution to the interfacial tension reduction is of enthalpic and not entropic origin (as (112) suggests), i.e., that it is due to the favorable energetics of the orientation of the copolymer blocks into their respective homopolymers and that entropic effects are second order. He suggests that (107) should be corrected by adding the contributions of the orientational entropy of the blocks and their entropy of localization. The latter was introduced by Shull and Kramer [77] by replacing γ 0 by \(\gamma \prime_0 = \gamma _0 + \sigma k_B T\ln \left[ {\left( {L_A + L_B } \right)/d\prime} \right]\). In the present analysis, the expression of Leibler [75, 76, 40] is utilized.

  2. 2.

    For polymer blends exhibiting lower critical solution temperature (LCST) behavior, e.g., the system polystyrene/poly(vinyl methyl ether), one may anticipate the opposite behavior for purely phenomenological reasons. Interfacial tension should increase with increasing temperature in the two-phase region since the tie lines become longer with increasing temperature in that case

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Acknowledgments

The author wishes to acknowledge H. Retsos for his help in the preparation of the present article. He would also like to thank I. Gancarz, N. Hadjichristidis, H. Watanabe, K. Adachi, J. W. Mays, M. Pitsikalis, S. Pispas, H. Iatrou, and K. Hong for synthesizing and kindly supplying the diblock copolymers and some of the homopolymers used in the previous works by the author on polymer–polymer interfacial tension. J. T. Koberstein is acknowledged for introducing the author to the area of polymer interfaces, as are T. P. Russell, S. K. Satija, C. F. Majkrzak, and G. Felcher with whom the author studied the structure of polymer interfaces. This research was sponsored by NATO’s Scientific Affairs Division in the framework of the Science for Peace Programmes (projects SfP-974173 and SfP-981438), by the Greek General Secretariat of Research and Technology in the framework of the ΠENEΔ Programme (projects 01EΔ587 and 03EΔ581), and by the European Union (projects G5RD-CT-2002-00834, NMP3-CT-2005-506621).

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  1. Institute of Electronic Structure and Laser, Foundation for Research and Technology – Hellas, 1527, 711 10, Heraklion, Crete, Greece

    Spiros H. Anastasiadis

  2. Department of Chemistry, University of Crete, 2208, 710 03, Heraklion, Crete, Greece

    Spiros H. Anastasiadis

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  1. Spiros H. Anastasiadis
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Correspondence to Spiros H. Anastasiadis .

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  1. Inst. Physikalische Chemie, Universität Mainz, Jakob-Welder-Weg 13, Mainz, 55099, Germany

    Bernhard A. Wolf

  2. Sekr. TK7, TU Berlin, Straße des 17. Juni 135, Berlin, 10623, Germany

    Sabine Enders

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Anastasiadis, S.H. (2010). Interfacial Tension in Binary Polymer Blends and the Effects of Copolymers as Emulsifying Agents. In: Wolf, B., Enders, S. (eds) Polymer Thermodynamics. Advances in Polymer Science, vol 238. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_2010_81

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