Dielectric spectroscopy techniques

This chapter concentrates on the results of DS study of the structure, dynamics, and macroscopic behavior of complex materials. First, we present an introduction to the basic concepts of dielectric polarization in static and time-dependent fields, before the dielectric spectroscopy technique itself is reviewed for both frequency and time domains. This part has three sections, namely, broadband dielectric spectroscopy, time-domain dielectric spectroscopy, and a section where different aspects of data treatment and fitting routines are discussed in detail. Then, some examples of dielectric responses observed in various disordered materials are presented. Finally, we will consider the experimental evidence of non-Debye dielectric responses in several complex disordered systems such as microemulsions, porous glasses, porous silicon, H-bonding liquids, aqueous solutions of polymers, and composite materials. 

Dielectric spectroscopy techniques are promising for numerous applications that require non-invasive, non-destructive, non-contact, and real-time measurements. Non-invasive measurements with gas, liquid, solid, and mixed samples are possible on distance scales from nanometers to meters and a frequency of excitation from microhertz to terahertz. The main advantages of fringing electric field dielectric sensors include one-side access to material under test, convenience of application... 

Dielectric spectroscopy techniques (3) represent an exception to this limitation. In fact, Senturia et al. (4) recently described a microdielectrometric method for in situ measurement of epoxy cure. Using a novel microdielectric probe, they studied isothermal cures of digylcidyl ether bisphenol-A (DGEBA) epoxy in which the low-frequency dielectric relaxation time, r, is correlated with the bulk viscosity (4). In this paper we report preliminary results on the utilization of a viscosity-dependent fluorescence probe as an alternative (and possibly complementary) new approach with potential for in situ monitoring of epoxy cure kinetics. We also report the observation of a unique fluorescence "self-probe capability of tetraglycidyl-diaminodiphenyl methane (TGDDM) epoxy which has not been reported previously. 

When rigid molecules process (case c) about the director at small 9 angles within the flat potential minimum they are more or less free. Therefore, frequency ( 2 correspond to a quite fast molecular motion and the precessimi contributes to both En and E (case c). All the three dispersion regions are observed by dielectric spectroscopy techniques [11]. 

Dielectric spectroscopy, also known as impedance spectroscopy, has been used for process analysis for some time, as it offers the ability to measure bulk physical properties of materials. It is advantageous to other spectroscopic techniques in that it is not an optical spectroscopy and is a noncontact technique, allowing for measurement without disturbing a sample or process. The penetration depth of dielectric spectroscopy can be adjusted by changing the separation between the sensor electrodes, enabling measurement through other materials to reach the substrate of interest. Because it measures the dielectric properties of materials, it can provide information not attainable from vibrational spectroscopy. 

Broadband Dielectric Spectroscopy provides a direct experimental access to the molecular relaxations of polymers over a broad frequency and temperature range. It is also especially suitable for the investigation of thin polymer films, because it does not suffer sensitivity loses with decreasing sample amount. This technique does require a special sample preparation for thin films, because of the need to have metal electrodes and good electrical contacts at both interfaces. Spin-coating, one of the most commonly employed methods for the preparation of... 

For thin polystyrene films annealed for 12 hours at 150 °C in high vacuum (10-6 mbar) and measured in a pure nitrogen atmosphere the dynamic glass transition was characterized using two experimental techniques capacitive scanning dilatometry and Broadband Dielectric Spectroscopy. Data from the first method are presented in Fig. 15a, showing the real part of the complex capacity at 1 MHz as a function of temperature for a thin PS film of 33 nm. 

Intercalated compounds offer a unique avenue for studying the static and dynamic properties of small molecules and macromolecules in a confined environment. More specifically, layered nanocomposites are ideal model systems to study small molecule and polymer dynamics in restrictive environments with conventional analytical techniques, such as thermal analysis, NMR, dielectric spectroscopy and inelastic neutron scattering. Understanding the changes in the dynamics due to this extreme confinement (layer spacing < Rg and comparable to the statistical segment length of the polymer) would provide complementary information to those obtained from traditional Surface-Force Apparatus (SFA) measurements on confined polymers (confinement distances comparable to Rp [36]. 

The presence of cooperative motion of chain segments present in intercalated polymer chains can be examined using various analytical techniques such as Differential Scanning Calorimetry (DSC), thermally stimulated current (TSC) and dielectric spectroscopy. DSC measurements on an intercalated PEO, (Mw= 100,000)/montmorillonite hybrid (20 wt. % polymer), indicated the absence of... 

Polymer silicate nanocomposites offer unique possibilities as model systems to study confined polymers or polymer brushes. The main advantages of these systems are (a) the structure and dynamics of nanoconfined polymer chains can be conveniently probed by conventional analytical techniques (such as scattering, DSC, NMR, dielectric spectroscopy, melt rheology) (b) a wide range of different polymers can be inserted in the interlayer or end-grafted to the silicate... 

Since the late nineteenth century, dielectric spectroscopy has been used to monitor dynamical properties of solid and liquid materials. At that time, dielectric measurements were performed either at a single frequency or in a very limited frequency range now, however, measurement technique and instrumentation have developed to such an extent that dielectric spectroscopy is today a well-established method to probe molecular dynamics over a broad range in frequency or time (cf. reviews by Johari [1], Bottcher and Bordewijk [34], Williams [35,36], and Kremer and Schonhals [37]), even with commercially available equipment. Including the latest developments, one can even say that nowadays dielectric spectroscopy is the only method that is fully able to realize the idea of 0- to 1-THz spectroscopy. In data sets that cover the range of up to 10 6—1013 Hz—that is, from ultra-low frequencies up to the far infrared—the full range of reorientational dynamics in... 

In order to actually cover 19 decades in frequency, dielectric spectroscopy makes use of different measurement techniques each working at its optimum in a particular frequency range. The techniques most commonly applied include time-domain spectroscopy, frequency response analysis, coaxial reflection and transmission methods, and at the highest frequencies quasi-optical and Fourier transform infrared spectroscopy (cf. Fig. 2). A detailed review of these techniques can be found in Kremer and Schonhals [37] and in Lunkenheimer [45], so that in the present context only a few aspects will be summarized. 

Figure 2. Different techniques used in dielectric spectroscopy in order to cover the full dynamic range of relaxational features at the glass transition for details see text. (From Ref. 37.)...

The characterization of the elastomer-filler interactions at a molecular level may be cairied out by spectroscopic techniques such as IR and NMR spectroscopy. X-ray and neutron scattering, dynamic mechanical and dielectric spectroscopy, and molecular dynamics simulations [6]. Up to now, the most comprehensive studies of silica filled PDMS [4, 7-22] and carbon black filled conventional rubbers [23] have been carried out by H [4, 7—20, 23], [21], and C NMR relaxation experiments [22],... 

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