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Polymer Composites with Molecular Fillers: Microscopic Views into Supramolecular Reinforcement

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Dynamics of Composite Materials

Part of the book series: Advances in Dielectrics ((ADVDIELECT))

Abstract

This chapter provides an overview of the insights that dielectric spectroscopy can provide into mechanisms of supramolecular reinforcement of polymer chains equipped with associating polar “sticky” groups. This situation features analogies to the pinning of polymer chains to attractive nanoparticles, but the dielectric response of the polar groups provides direct access to the dynamics of the sticky sites. This is of potential use in elucidating the molecular origin of the viscoelastic properties of such materials. Analogies and differences between systems composed of defined binary associates versus large aggregates are discussed, and ambiguities as well as open challenges in interpreting the experimental results are highlighted.

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Abbreviations

BIIR:

Brominated isobutylene isoprene rubber (also: butyl rubber)

BLrN:

Bond lifetime renormalization

\(\Delta H_\mathrm {st}\) :

Reaction enthalpy for sticky bond formation

\(c_x\) :

Number/mole concentration of species x

\(\Delta \varepsilon \) :

Dielectric strength of a relaxtion

BDS:

Broadband dielectric spectroscopy

DP:

Degree of polymerization

DSC:

Differential scanning calorimetry

\(\varepsilon ^\prime \), \(\varepsilon ^{\prime \prime }\):

Real and imaginary part of the complex dielectric function

\(\epsilon _\mathrm {b}\) :

Microscopic energy barrier for sticker association/dissociation

\(E_\mathrm {a}^\mathrm {st}\) :

Activation energy for sticker dissociation

HN:

Havriliak-Negami (fitting function)

ILM:

Interfacial layer model

IR:

Infrared (spectroscopy)

\(J(\tau _\mathrm {open})\) :

Number of returns of a free sticker

\(K_\mathrm {a/d}\) :

Association/dissociation equilibrium constant

\(k_+\) :

Association rate

\(k_-\) :

Dissociation rate

\(\mu \) :

Electric dipole moment, mostly in Debye (1 D = 3.336\(\times \)10\(^{-30}\) C\(\cdot \)m)

MWS:

Maxwell-Wagner-Sillars (interfacial polarization process)

\(\bar{n}\) :

(mole) number density

\(\tau _\alpha ^*\) or \(\tau _{\alpha _2}\):

Dielectric relaxation time associated with sticky groups

\(\tau _\mathrm {d}^*\) :

Timescale for sticker dissociation (\(=1/k_-\))

\(\tau _\mathrm {CR}\) :

Dielectric relaxtion time related to sticker clusters; unknown origin

\(\tau _\mathrm {open}\) :

Timescale of free-sticker diffusion

\(\tau _\mathrm {rot}\) and \(\tau _\mathrm {rot}^\prime \):

Rotational correlation time of a free sticker and a sticker pair, resp.

\(\tau _\mathrm {st}^*\) :

Rheologically relevant relaxation time of a sticky chain segment

\(T_\mathrm {g}\) :

Glass transition temperature

PB:

Polybutadiene

PDMS:

Polydimethylsiloxane

PI:

Polyisoprene

PIB:

Polyisobutylene

\(\omega \) :

Angular frequency in rad/s

SAXS:

Small-angle X-ray scattering

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Acknowledgements

I am indebted to all members of the groups of Ralph Colby and Jim Runt for their hospitality during my sabbatical at Penn State University in spring 2018, teaching an old NMR dog new dielectric tricks. I particularly thank Ciprian Iacob for guiding my first steps into hands-on dielectric spectroscopy, as well as Aijie Han and Josh Bostwick for sustained support. Ralph’s critical views on ambiguous data and numerous discussions are highly appreciated. I also thank Thomas Thurn-Albrecht and Klaus Schröter for valuable comments and suggestions.

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Authors and Affiliations

  1. Institut für Physik – NMR, Martin-Luther-Universität Halle-Wittenberg, Betty-Heimann-Str. 7, 06120, Halle (Saale), Germany

    Kay Saalwächter

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  1. Kay Saalwächter
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Correspondence to Kay Saalwächter .

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  1. Bundesanstalt für Materialforschung und -prüfung (BAM), Berlin, Berlin, Germany

    Andreas Schönhals

  2. Bundesanstalt für Materialforschung und -prüfung (BAM), Berlin, Germany

    Paulina Szymoniak

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Saalwächter, K. (2022). Polymer Composites with Molecular Fillers: Microscopic Views into Supramolecular Reinforcement. In: Schönhals, A., Szymoniak, P. (eds) Dynamics of Composite Materials. Advances in Dielectrics. Springer, Cham. https://doi.org/10.1007/978-3-030-89723-9_6

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