Dielectric Relaxation Spectroscopy Data Research Articles

Significant Interfacial Dielectric Relaxation of Covalently Bonded Ice-Hydrogels.

Hydrogels are composed of a three-dimensional network of cross-linked hydrophilic polymer chains and large amounts of water. The physicochemical properties of the polymer-water interface in hydrogels draw our attention. Due to the complex structure of hydrogel systems, it is still a challenge to investigate the interfacial layer properties of hydrogels through experiments. In this work, we investigate the properties of the covalently bonded chitosan-based ice-hydrogels interfacial layer by dielectric relaxation spectroscopy (DRS) techniques in the presence of avoided electrode polarization. The DRS data exhibit that the polymer-water interfacial layer has a strong dielectric signal response, which indicates that a large number of polar electric dipoles or polar molecules may be contained in the interfacial layer. The variable temperature dielectric relaxation behavior of a series of chitosan-base ice-hydrogels showed that the value of dielectric activation energy for different water contents is about 180 kJ/mol, which is much larger than that of the polymer and ice phases, suggesting a strong coupling of polar electric dipoles within the interfacial layer. This work demonstrates the important role of the polymer-water interface in covalently bonded hydrogels, which will provide assistance in the design and application of covalently bonded hydrogels.

Miscibility of Poly(Methyl Methacrylate) and Poly(Vinylidene Fluoride) Examined by Thermally Stimulated Depolarization Current and Dielectric Relaxation Spectroscopy

Samples of poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF) and melt blended PMMA/PVDF with weight ratios 4/1 and 3/2 were characterized by thermally stimulated depolarization currents (TSDC) in the temperature interval 123-303 K and by dielectric relaxation spectroscopy (DRS) in the frequency window 10−2 − 106 Hz in the temperature interval 153-423 K. The TSDC thermograms and DRS profiles of the samples showed the two types of conducnivity – non-cooperative and cooperative. The experimental DRS data in the vicinity of the glass transition temperature, Tg, were quantitatively fitted to the Havriliak-Negami function and values of the maximum relaxation time were fitted to the Vogel-Tammann-Fulcher equation. Higher values of the strength index D, of the dielectric relaxation strength Δε and of the σ ac conductivity for the binary blends were considered as experimental evidence for nanoscale composition heterogeneities originating from strong specific interactions between the PMMA and PVDF. Therefore, we suggest the PMMA/PVDF blends will be usefull as effective materials for the manufacture of lithium-ion batteries, electrostatic capacitors with superior energy storage performance, polymer composite electrolytes for solar cells, etc.

The Effect of a Copolymer of Ethylene and Vinyl Acetate on the Formation of the Structure and the Processing Properties of Olefinic Thermoplastic Elastomers

Optical microscopy and dielectric relaxation spectroscopy (DRS) were used to study the structure of dynamically vulcanised mixes based on polypropylene, ethylenepropylenediene rubber, and copolymers of ethylene and vinyl acetate (Levapren 400, 600, 700). For the microscopic investigations, we used a complex consisting of a Leica DM-2500 optical microscope, a DFC 420C cooling chamber, and a special computer desk. DRS data were obtained on a BDS 89 instrument (NovoControl) at temperatures ranging from −150 to +100°C at a heating rate of 2°C/min and a frequency of 110 Hz. The influence of the content of Levapren and the proportion of vinyl acetate in its composition on the morphology and processing properties of olefinic thermoplastic vulcanisates (TPVs) was investigated. The combination of the discovered changes in the fine structure and DRS data indicate the preferential interaction of Levapren with the rubber component. The evolution of the morphology of the TPVs with increase in the volume fraction of vinyl acetate is not monotonic, which is consistent with the nature of change in the physicomechanical properties of the TPVs. Combined analysis of the morphological characteristics and processing properties of TPVs showed that, to achieve high values of the deformation and strength properties, a uniform distribution and high polydispersity of the ingredients are necessary. Increase in the elastic properties of the material is ensured by modification of the polypropylene phase to form fibrillar structures, while the flow of TPEs that is necessary for processing is facilitated by modification of the rubber phase.

Dielectric relaxations of nanocomposites composed of HEUR polymers and magnetite nanoparticles

We investigate the dynamics of nanocomposites composed of hydrophobically modified ethoxylated urethanes (HEUR) and magnetite nanoparticles (MNPs) as dry films. We employed dielectric relaxation spectroscopy (DRS) in combination with differential scanning calorimetry (DSC) and thermally stimulated depolarization currents (TSDC). The three techniques reveal a strong heterogeneity of the matrix of the nanocomposites, consisting of (i) a crystalline poly(ethyleneoxide) PEO bulk phase, (ii) an amorphous PEO portion, and (iii) small PEO crystallites which experience different constraints than the PEO bulk phase. TSDC and DRS reveal a very high direct current (DC)-conductivity of the pure matrix, which increases with MNPs concentration. The increase of the DC-conductivity is not related to an increase of the segmental mobility, but most likely to the change of the morphology of the hydrophobic domains of the polymer matrix, due to the formation of large MNPs clusters. Indeed, the MNPs neither influence the segmental dynamics of the polymer nor the phase behavior of the polymer matrix. The addition of MNPs slightly increases the activation energy related to the γ-relaxation of the polymer. This effect might be related to the changes in nano-morphology as demonstrated by the slight increase of the degree of crystallinity. The analysis of the DRS data with the electrical modulus M″(ω) and the derivative ε″der formalism allow us to identify a low-frequency process in addition to the conductivity relaxation. This low-frequency dispersion is also revealed by TSDC. It is most likely related to the Maxwell-Wagner-Sillars relaxation, which typically occurs in systems which feature phase separation. The detailed investigation of the dielectric properties of these novel nanocomposites with increasing MNPs concentration will be useful for their practical application, for example as absorbers of electromagnetic waves.

Multi-stage freezing of HEUR polymer networks with magnetite nanoparticles.

We observe a change in the segmental dynamics of hydrogels based on hydrophobically modified ethoxylated urethanes (HEUR) when hydrophobic magnetite nanoparticles (MNPs) are embedded in the hydrogels. The dynamics of the nanocomposite hydrogels is investigated using dielectric relaxation spectroscopy (DRS) and neutron spin echo (NSE) spectroscopy. The magnetic nanoparticles within the hydrophobic domains of the HEUR polymer network increase the size of these domains and their distance. The size increase leads to a dilution of the polymers close to the hydrophobic domain, allowing higher mobility of the smallest polymer blobs close to the "center". This is reflected in the decrease of the activation energy of the β-process detected in the DRS data. The increase in distance leads to an increase of the size of the largest hydrophilic polymer blobs. Therefore, the segmental dynamics of the largest blobs is slowed down. At short time scales, i.e. 10(-9) s < τ < 10(-3) s, the suppression of the segmental dynamics is reflected in the α-relaxation processes detected in the DRS data and in the decrease of the relaxation rate Γ of the segmental motion in the NSE data with increasing concentration of magnetic nanoparticles. The stepwise (multi-stage) freezing of the small blobs is only visible for the pure hydrogel at low temperatures. On the other hand, the glass transition temperature (Tg) decreases upon increasing the MNP loading, indicating an acceleration of the segmental dynamics at long time scales (τ∼ 100 s). Therefore, it would be possible to tune the Tg of the hydrogels by varying the MNP concentration. The contribution of the static inhomogeneities to the total scattering function Sst(q) is extracted from the NSE data, revealing a more ordered gel structure than the one giving rise to the total scattering function S(q), with a relaxed correlation length ξNSE = (43 ± 5) Å which is larger than the fluctuating correlation length from a static investigation ξSANS = (17.2 ± 0.3) Å.

Thermally stimulated depolarization current and dielectric spectroscopy used to study dipolar relaxations and trap level distribution in PMMA polymer

In this work, thermally stimulated depolarization current (TSDC) and dielectric relaxation spectroscopy (DRS) techniques were performed in complementarities to characterize the dielectric relaxation processes in poly(methylmethacrylate) (PMMA) polymer. Three relaxations were highlighted. Based on correlation between TSDC and DRS data, they were attributed respectively to dipolar β and α relaxations as well as interfacial ρ relaxation. New experimental procedure of fractional polarization was used to investigate space charge trap depth distribution within the band-gap of PMMA. Then the individual peaks were fitted to Bucci–Fieschi model, to evaluate the relaxation parameters. The obtained values were discussed in correlation to those evaluated from DRS data fitted to Havriliak–Negami and Arrhenius models. The various observed peaks in the thermograms are discussed on the basis of space charge polarization. The trap energies were evaluated from the fit to the Bucci–Fuschi model. Similarly other parameters such as relaxation time and charge release are evaluated.

Understanding the Ion Jelly Conductivity Mechanism

The properties of the light flexible device, ion jelly, which combines gelatin with an ionic liquid (IL) were recently reported being promising to develop safe and highly conductive electrolytes. This article aims for the understanding of the ion jelly conductive mechanism using dielectric relaxation spectroscopy (DRS) in the frequency range 10(-1)-10(6) Hz; the study was complemented with differential scanning calorimetry (DSC) and pulsed field gradient nuclear magnetic resonance (PFG NMR) spectroscopy. The room temperature ionic liquid 1-butyl-3-methylimmidazolium dicyanamide (BMIMDCA) used as received (1.9% w/w water content) and with 6.6% (w/w) of water content and two ion jellies with two different ratios BMIMDCA/gelatin/water % (w/w), IJ1 (41.1/46.7/12.2) and IJ3 (67.8/25.6/6.6), have been characterized. A glass transition was detected by DSC for all materials allowing for classifying them as glass formers. For the ionic liquid, it was observed that the glass transition temperature decreases with the increase of water content. While in subsequent calorimetric runs crystallization was observed for BMIMDCA with negligible water content, no crystallization was detected for any of the ion jelly materials upon themal cycling. To the dielectric spectra of all tested materials, both dipolar relaxation and conductivity contribute; at the lowest frequencies, electrode and interfacial polarization highly dominate. Conductivity, which manifests much more intensity relative to dipolar reorientations, strongly evidences subdiffusive ion dynamics at high frequencies. From dielectric measures, transport properties as mobility and diffusion coefficients were extracted. Data treatment was carried out in order to deconvolute the average diffusion coefficients estimated from dielectric data in its individual contributions of cations (D(+)) and anions (D(-)). The D(+) values thus obtained for IJ3, the ion jelly with the highest IL/gelatin ratio, cover a large temperature range up to room temperature and revealed excellent agreement with direct measurements from PFG NMR, obeying to the same VFT equation. For BMIMDCA(6.6%water), which has the same water amount as IJ3, the diffusion coefficients were only estimated from DRS measurements over a limited temperature range; however, a single VFT equation describes both DRS and PFG NMR data. Moreover, it was found that the diffusion coefficients and mobility are similar for the ionic liquid and IJ3, which points to a role of both water and gelatin weakening the contact ion pair, facilitating the translational motion of ions and promoting its dissociation; nevertheless, it is conceivable the existence of a critical composition of gelatin that leads to those properties. The VFT temperature dependence observed for the conductivity was found to be determined by a similar dependence of the mobility. Both conductivity and segmental motion revealed to be correlated as inferred by the relatively low values of the decoupling indexes. The obtained results show that ion jelly could be in fact a very promising material to design novel electrolytes for different electrochemical devices, having a performance close to the IL but presenting an additional stability regarding electrical measurements and resistance against crystallization relative to the bulk ionic liquid.

Glass transition and segmental dynamics in poly(dimethylsiloxane)/silica nanocomposites studied by various techniques

We report new results on segmental dynamics and glass transition in a series of poly(dimethylsiloxane) networks filled with silica nanoparticles prepared by sol-gel techniques, obtained by differential scanning calorimetry (DSC), thermally stimulated depolarization currents (TSDC), broadband dielectric relaxation spectroscopy (DRS) and dynamic mechanical analysis (DMA). The nanocomposites are characterized by a fine dispersion of 10nm silica particles and hydrogen bonding polymer/filler interactions. The first three techniques indicate, in agreement with each other, that a fraction of polymer in an interfacial layer around the silica particles with a thickness of 2–3nm shows modified dynamics. The DSC data, in particular measurements of heat capacity jump at Tg, are analyzed in terms of immobilized polymer in the interfacial layer. The dielectric TSDC and DRS data are analyzed in terms of slower dynamics in the interfacial layer as compared to bulk dynamics. We employ a special version of TSDC, the so-called thermal sampling (TS) technique, and provide experimental evidence for a continuous distribution of glass transition temperatures (Tg) and molecular mobility of the polymer in the interfacial layer, which is consistent with the DRS data. Finally, DMA results show a moderate slowing down of segmental dynamics of the whole polymer matrix (increase of glass transition temperature by about 10K as compared to the pure matrix).

Location and de-trapping energy of sodium ions in dehydrated X and Y faujasites determined by dielectric relaxation spectroscopy

Both the location and the de-trapping energy Δ E of the extraframework sodium cations embedded in Na 56Y and Na 96X zeolites are investigated by means of dielectric relaxation spectroscopy (DRS). It is shown that the Na + cations are distributed into three different types of crystallographic sites, with a respective occupancy established by comparing our DRS data to those previously obtained from simulation. Then, the de-trapping energy of the Na + cations embedded in each crystallographic site is determined and analysed in the light of the structural feature of the site. The difference between the de-trapping energy of the different crystallographic sites in Na 56Y and Na 96X is thus interpreted using simple qualitative models based on electronegativity and cation/cation repulsion. It is thus shown that the consideration of this later parameter is essential to explain the rearrangement of the energy level of each cation site when a critical Si/Al ratio is reached.

Curing of an epoxy resin modified with poly(methylmethacrylate) monitored by simultaneous dielectric/near infrared spectroscopies

Simultaneous dielectric and near infrared measurements have been performed in “real-time” to follow polymerisation reactions on blends of a diglycidyl ether of bisphenol-A epoxy resin with 4,4 ′-diaminodiphenylmethane hardener and different amounts of poly(methylmethacrylate) as modifier. The effect of the modifier amount on the polymerisation reactions has been studied, as well as that of the curing temperature. Epoxy and amine conversions have been followed by near infrared spectroscopy (NIR), while changes in molecular mobility in the reaction mixture have been analysed by dielectric relaxation spectroscopy (DRS). Evolutions of ionic conductivity and α-relaxation have been analysed and vitrification times have been obtained. The relaxational behaviour has been analysed through curing in the frequency domain, being the change of the main relaxation indicative of the cure reaction advancement. DRS data are also presented as complex impedance Z( ω). Vitrification times, obtained by dielectrometry have been compared with those obtained by rheological measurements and gelation times obtained by NIR have been compared with those obtained by solvent extraction.

Dielectric and dynamic mechanical relaxation behaviour of poly(ethylene 2,6-naphthalene dicarboxylate). II. Semicrystalline oriented films

The dielectric and dynamic mechanical behaviour of bi-stretched non-treated and annealed semicrystalline poly(ethylene 2,6-naphthalene dicarboxylate) (PEN) films are studied as a function of different morphologies obtained by thermal treatments at temperatures close to the melting temperature of a semicrystalline film. Differential scanning calorimetry (DSC) shows that the glass transition temperatures do not change significantly with the thermal treatment for bi-stretched films. However, the melting temperatures and the degree of crystallinity increase with the value of annealing temperature. Both dielectric relaxation spectroscopy (DRS) and dynamic mechanical analysis (DMA) display three relaxation processes. In order of decreasing temperature, can be observed: the α-relaxation due to the glass transition, the β ∗-process assigned to cooperative molecular motions of the naphthalene groups which aggregate and the β-relaxation due to local fluctuations of the carbonyl groups. The α-relaxation process shifts to higher temperatures for the 250 and 260 °C treated bi-stretched semicrystalline samples compared to the sample thermally treated at 240 °C according to DRS data but shifts to lower temperatures according to the DMA measurements for the three annealed samples. This discrepency results from the different sensitivity of each methods with regards to the release of orientation. At a fixed frequency the temperature associated to β ∗-relaxation is lower for the non-treated bi-stretched semicrystalline samples than for the treated ones using DMA but no difference can be seen in DRS. The associated apparent activation energies are rather high which suggest cooperative motions. It is assumed that the orientation of the samples prevents coupling between the naphthalene groups due to the stretched chain configuration in the amorphous phase. The activation energy for the β-process given by DRS is independent of the thermal treatment and the value agrees with those found for poly(ethylene terephthalate) (PET) and amorphous PEN. Evidence of the decrease of orientation in the sample with thermal treatment can be seen via the onset of mobility, both by DRS and DMA. Thus, the orientation induces a greater change of properties compared to the crystalline samples obtained from the thermal treatment of an amorphous sample. Finally, a three phase model is proposed since there is evidence of a rigid amorphous phase present in PEN biaxially stretched samples which was favoured by the dependence of dielectric relaxation strengths on the degree of crystallinity for the β ∗- and α-relaxation.

Dielectric relaxation of the alternating terpolymers of ethylene, propylene, and carbon monoxide

The alternating terpolymers of ethylene, propylene, and carbon monoxide were characterized by wide-angle x-ray scattering (WAXS), differential scanning calorimeter (DSC), thermally stimulated depolarization currents, and dielectric relaxation spectroscopy (DRS). At room temperature, the terpolymers were x-ray amorphous; however, the existence of weak endothermal effects over fairly broad temperature intervals above the glass transition suggested that they should be classified as “microcrystalline” (in a sense that the ultimate level of crystallinity lies beyond the resolution limits of ordinary WAXS instruments). The DRS data in the temperature intervals of α- and sub-glass relaxations were fitted quantitatively to the Havriliak–Negami equation. The characteristic parameters for the α-relaxation were consistent with classification of terpolymers as relatively fragile glass formers; however, their high fragility was attributed to steric constraints to the motion of chain dipoles by the residual network of microcrystals. Strong asymmetry of the dielectric sub-glass relaxation was regarded as additional experimental evidence for the interference of the spatial network of microcrystallites with the motion (in this case, noncooperative) of chain segments.

Local Dynamics of Bismaleimide Adhesives in an Aggressive Environment

Molecular aspects of chemical and physical changes in bismaleimide (BMI) adhesive joints caused by absorbed moisture were investigated. The focus was on the early (pre-damage) stage that precedes the formation of voids and microcracks. Local dynamics were investigated by broad-band dielectric relaxation spectroscopy (DRS) and the changes in the chemical state of the matter were monitored by Fourier transform infrared spectroscopy (FTIR). Absorbed water interacts with the BMI network and gives rise to a fast relaxation process (termed γ*), characterized by an increase in the dielectric relaxation strength, an Arrhenius temperature dependence of the average relaxation time, and an activation energy of 50 kJ/mol. The γ* dynamics are slower than the relaxation of bulk liquid water because of the interactions between the absorbed water and various sites on the network (the ether oxygen, the hydroxyl group, the carbonyl group, and the tertiary amine nitrogen). One particularly significant finding is that the average relaxation time for the γ* process above 20°C is of the order of nanoseconds or less and, hence, the detection and monitoring of this process hinges upon the ability to perform high precision DRS at frequencies above 1 MHz. This is an important consideration in the ongoing efforts aimed at the implementation of DRS as a non-destructive inspection (NDI) tool for adhesive joints. FTIR spectra reveal the presence of non hydrogen-bonded water and hydrogen-bonded water, the latter bonded to one and/or two sites on the BMI network. A good agreement was found between the calculated ratio of non hydrogen-bonded to total absorbed water from DRS and FTIR data.

Changes in molecular dynamics during the bulk polymerisation of an epoxide/boroxine mixture as studied by dielectric relaxation spectroscopy, revealing direct evidence for a floor temperature for reaction

Real-time dielectric relaxation spectroscopy (DRS), has been used to monitor changes in the dynamics of chain dipoles and of ions during the bulk polymerisation of an epoxide/boroxine system at different reaction temperatures T R in the range 60–120°C. For T R<72°C the dielectric α-process moved to ultra-low frequencies indicating the formation of a chemically unstable glass. For T R>72°C the process moved from high frequencies to settle at audio or higher frequencies, giving a loss peak independent of time that indicated the formation of a chemically stable elastomer. We analysed our results in terms of changes in molecular mobility in the reaction mixture with time and have determined the floor-temperature T F below which a glass is formed and above which an elastomer is formed. The DRS data were also presented as complex impedance Z( ω) which emphasises changes of ionic conductance during reaction. Below T F the peak in the loss impedance Z″ m moved to ultra-low frequencies during reaction in a time-scale far shorter than that for the dielectric loss peak ε″ m. Comparison of the two representations of data made well above T F show that the Z″ data become independent of time before the ε″ data. DRS data presented as dielectric permittivity ε( ω) provides a good indicator of glass-formation below T F and of elastomer-formation above T F. Our data are considered in relation to the TTT-diagram of Gillham and coworkers that describes the onset of gelation, glass-formation and elastomer-formation during cure and we extend this diagram to describe how T g evolves with time for different values of T R.