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Broadband Dielectric Spectroscopy on Polymer Blends

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Polymer Blends Handbook

Abstract

In this chapter broadband dielectric spectroscopy (BDS) is employed to polymeric blend systems. In its modern form BDS can cover an extraordinary broad frequency range from 10−4 to 1012 Hz. Therefore, molecular and collective dipolar fluctuations, charge transport, and polarization effects at inner phase boundaries can be investigated in detail including its temperature dependence. In the first part of the chapter, the theoretical basics of dielectric spectroscopy are briefly introduced covering both static and dynamic aspects. This section is followed by short description of the various experimental techniques to cover this broad frequency range. To provide the knowledge to understand the dielectric behavior of polymeric blend systems, the dielectric features of amorphous homopolymers are discussed in some detail. This concerns an introduction of the most important relaxation processes observed for these polymers (localized fluctuations, segmental dynamics related to the dynamic glass transition, chain relaxation), a brief introduction to the conductivity of disordered systems as well as polarization effects at phase boundaries. Theoretical models for each process are shortly discussed. In the last paragraph the dielectric behavior of polymer blends is reviewed where special attention is paid to binary systems for the sake of simplicity. In detail the dielectric behavior of binary miscible blends is described. The two most important experimental facts like the broadening of the dielectric relaxation spectra and the dynamic heterogeneity of the segmental dynamics are addressed in depth. Appropriate theoretical approaches like the temperature-driven concentration fluctuation model and the self-concentration idea are introduced.

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Authors and Affiliations

  1. BAM Federal Institute for Materials Research and Testing, Unter den Eichen 87, Fachbereich 7.5, 12205, Berlin, Germany

    Huajie Yin

  2. BAM Federal Institute for Materials Research and Testing, Unter den Eichen 87, Fachbereich 6.9, 12205, Berlin, Germany

    Andreas Schönhals

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  1. Huajie Yin
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Correspondence to Andreas Schönhals .

Editor information

Editors and Affiliations

  1. Industrial Materials Institute, National Research Council of Canada, Boucherville, Québec, Canada

    Leszek A. Utracki

  2. Department of Chemistry and Fire Retardant Research Facility, Marquette University, Milwaukee, Wisconsin, USA

    Charles A. Wilkie

List of Important Symbols and Abbreviations

aT

Shift factor

C

Concentration

C1, C2

Parameters of the WLF equation

D

Dielectric displacement

E

Electric field strength

EA, ΔE

Activation energy, barrier heights

f

Frequency

fi

Relaxation rate at maximal loss, i = β, α, n

f∞i

Preexponential factor, i = β, α, n

Φi

Volume fraction

ϕi

Weight fraction

g, gintra

Dipolar correlation coefficients

ΔGM

Free energy of mixing

Γ*

Reflection coefficient

I, J

Current, Current density

kB

Boltzmann constant, kB = 1.380662 10−23 J K−1; kB = R/NA

M, MW

Molecular weight, weight average

NA

Avogadro number (NA = 6.022 1023 mol−1)

R

Gas constant R = 8.314 kJ mol−1

SC

Configurational entropy

ΔSM

Mixing entropy

σ*, σ′, σ′

Complex conductivity, real and imaginary part

T

Temperature

T0

Vogel temperature, ideal glass transition temperature

Tg

Glass transition temperature

tan δ

Dielectric loss tangent

β, γ

Shape parameter of the HN function

ε0

Permittivity of vacuum (ε0 = 8.854 10−12 As V−1 m−1)

ε*, ε′, ε′

Complex dielectric function, real and imaginary part

Δεi

Dielectric relaxation strength, i = β, α, n,

ζ

Monomeric friction coefficient

ξ

Correlation length

κ

Flory/Huggins interaction parameter

μ

Dipole moment

ω

Angular frequency (ω = 2*π*f)

τ

Relaxation time

τHN

Relaxation time of the HN function

τe

Time constant for conduction

PEO

Poly(ethylene oxide)

PI

Cis-1,4-Polyisorene

PMMA

Poly(methyl methacrylate)

PPG

Poly(propylene glycol)

PS

Polystyrene

PVAC

Poly(vinyl acetate)

PVME

Poly(vinyl methylether)

PoClS

Poly(o-chlorostyrene)

PVC

Poly(vinyl chloride)

U

Voltage, different meanings

Z *S (ω); Z *R (ω)

Sample impedance; Reference impedance

<…>

Correlation function; Averaged quantities

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Yin, H., Schönhals, A. (2014). Broadband Dielectric Spectroscopy on Polymer Blends. In: Utracki, L., Wilkie, C. (eds) Polymer Blends Handbook. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-6064-6_14

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