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1.
Highly thermostable low-k polymer films with potential applications as dielectric materials in microelectronic industry were synthesized starting from 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride and various diamines. A polyetherimide/silica nanocomposite film was obtained using methyltriethoxysilane as precursor of inorganic phase. The chemical structure was confirmed by FTIR and 1H NMR spectroscopy. Water vapor's sorption capacity, thermal stability, glass transition temperature, thermal diffusivity, specific heat, thermal conductivity, and dielectric characteristics of the films were determined. All the films exhibited excellent thermal stability, with an initial decomposition temperature in the range of 500–530°C. They showed low dielectric constant of 1.98–2.86 and low dielectric loss of 0.0037–0.011, at a frequency of 1 Hz and room temperature. The subglass γ- and β-relaxations, primary α-relaxation, and conductivity relaxation processes were discussed according to the chemical structure of the samples. Quantitative structure–property relationship (QSPR) study was conducted, and linear regression models were formulated to describe the causal relationships between different parameters and polyetherimide properties.  相似文献   

2.
Broadband dielectric relaxation spectra are reported on a range of poly(ether imide) polymers in which the chemical structure of the diamine used to create the polymer is systematically varied with the anhydride structure based on 2,2‐bis‐[4‐(3′,4′‐dicarboxyphenoxy)phenyl]hexafluoroisopropylidine dianhydride. In all the polymers examined, a dipole relaxation was observed below room temperature. The magnitude and activation energy associated with the relaxation process varied with the chemical structure reflecting the effects of steric hindrance on the conformational change associated with the N? C and C? O? C linkages. Values of the activation energies varied between 29 and 34 kJ/mol?1, and are consistent with the observed relaxation being associated with constrained local oscillatory motions of small elements of the polymer backbone. The glass transition temperatures of these polymers are in the range 195–243°C and are associated with the large scale motion of the polymer backbone. Changes in the backbone structure influence the extent of inter chain–chain interaction and are reflected in the amplitude of the relaxation process and the high frequency limiting dielectric permittivity ε values which are important when these polymers are used in thin film electronic applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41684.  相似文献   

3.
Dynamic mechanical analysis and dielectric relaxation spectra of exfoliated nano graphite reinforced flouroelastomer composites were used to study their relaxation behavior as a function of temperature (−80°C to +40°C) and frequency (0.01 to 105 Hz). The effect of filler loadings on glass transition temperature was marginal for all the composites and Tg value was in the narrow range of 7.8–8.4°C, which has been explained on the basis of relaxation dynamics of polymer chains in the vicinity of fillers. Strain‐dependent dynamical parameters were evaluated at dynamic strain amplitudes of 0.01–10%. The nonlinearity in storage modulus has been explained on the concept of filler‐polymer interaction and filler aggregation of the nano graphite platelets. The variation in real and complex part of impedance with frequency has been studied as a function of filler. The percolation of the nano graphite as studied by conductivity measurements is also reported. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers.  相似文献   

4.
This study presents an investigation on polyimides derived from a unfunctionalized symmetric cyclopentyl‐containing alicyclic cardo‐type dianhydride with ester linkage 1,1‐bis(4‐(3,4‐dicarboxylbenzoyloxy)phenyl)cyclopentylene dianhydride (BDPCP) that was readily accessed starting from cyclopentanone through two steps in high yield. Two series of polyimides, Cardo‐type series (CPI‐x) and analogous aromatic series (ArPI‐x) were prepared from condensation of BDPCP and aromatic 3,3′,4,4′‐Oxydiphthalic dianhydride with four aromatic diamines, respectively. Comparative studies revealed that CPI polymers show more favorable properties including better solubility in organic solvents, higher transparency with lower cut‐off wavelength (λ0) ranging in 395–375 nm than 425–405 nm, lower water absorption ranging in 0.66–1.14% and surface energy 23.71–32.77 mN/m than 1.01–1.28% and 29.52–41.99 mN/m of ArPI analogs. Meanwhile, CPI series exhibit considerable mechanical properties with tensile strengths ranging in 87.6–102.9 MPa, elongations at break 6.6–8.9%. Owing to the moderate strain in cyclopentyl ring, CPI series retain good thermal properties with the glass transition temperature (Tg) in the range of 217–271°C. Dynamic dielectric measurement revealed that Cardo‐type dianhydride BDPCP endows CPI‐4 film with lower dielectric constant (ε′) 3.34 at 1 MHz and 25°C and dielectric loss (ε′′) 0.0064 at 1 kHz and 25°C than 3.49 and 0.013 for ArPI‐4 film. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42670.  相似文献   

5.
Polycrystalline BiFeO3 was synthesized at 400°C–700°C. Distinctive difference in the magnetic and dielectric properties was observed between the samples sintered at 400°C–500°C and those sintered at 600°C–700°C. The former showed ferromagnetic‐like hysteresis loops with an increased magnetization of 0.54 emu/g, whereas the later showed linear loops with a small magnetization of 0.065 emu/g. Although X‐ray did not identify any secondary phase, the suspected trace of some magnetic phase (Fe3O4) in the samples was conceded by the occurrence of an exchange bias. The difference in dielectric response between the two groups of samples arose mainly from a different conductivity at the grain boundaries. Owing to Fe3O4 coating at grain surface, the 400°C–500°C sintered samples behaved like a single parallel R–C circuit, whereas the dielectric response of the samples sintered at 600°C–700°C was represented by a series of two parallel R‐C units for grains and grain boundaries, respectively. Two dielectric relaxation peaks observed at <700 Hz and 0.3~6 MHz in the high‐temperature sintered samples were attributed to the Maxwell–Wagner relaxation and electron hopping, respectively.  相似文献   

6.
Poly(methyl methacrylate) doped with fluorescent perylene dye was prepared by both radical polymerization of methyl methacrylate and solvent casting from polymer solutions. The samples were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, electrical conductivity, and dielectric properties. Both conductivity and dielectric properties were measured in the temperature range 303–433 K and the frequency range 103 to 5 × 106 Hz. The results show that the direct‐current electrical conductivity increased by increasing dye content in solvent‐cast samples, whereas it decreased radically polymerized samples. The results of alternating‐current conductivity suggest electron hopping between filled and empty localized states. The study of dielectric properties showed two relaxation peaks corresponding to the dipole segmental and dipole group losses. Explanations based on the polymer free volume and acid–base interactions were proposed to examine the influence of the sample preparation and perylene dye concentration on the glass‐transition temperature and dielectric relaxation of the samples. The obtained results recommend the thermal and molecular stability of luminescent solar concentrator (LSC) matrices prepared by radical polymerization over those prepared by solvent casting. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 793–805, 2003  相似文献   

7.
Dielectric properties and ac electrical conductivity of Acrylonitrile Butadiene Rubber‐poly(vinyl chloride)/Graphite Composite were studied at different frequencies (102?106 Hz) in the temperature range (298–423 K). The results show that the dielectric constant (ε′), dielectric loss (ε″), ac electrical conductivity (σac) and, the electric modulus are strongly dependent on the frequency and temperature. The dielectric constant ε′ increases with temperature and decreases with frequency, whereas the dielectric loss ε″ displays a broad maximum peak whose position shifts with temperature to a higher frequency region. Cole–Cole diagrams have been used to investigate the frequency dependence of the complex impedance at different temperature and graphite loading. Interfacial or Maxwell‐Wagner‐Sillars relaxation process was revealed in the frequency range and temperature interval of the measurements, which was found to follow the Havriliak–Negami approach for the distribution of relaxation times. At constant temperature, the frequency dependence of ac conductivity was found to fit with the established equation σac(ω) = Aωs quite well. The values of S for the investigated samples lie between 0.88 and 0.11. The conduction mechanism of ac conduction was discussed by comparing the behavior of the frequency exponent S(T) with different theoretical models. It was found that the correlated barrier hopping (C.B.H.) is the dominant conduction mechanism. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

8.
Poly(3‐hydroxybutyrate), PHB, is a widely distributed carbon storage polymer among prokaryotes including Rhizobium. Capacities of Rhizobium etli R13 to produce the bioplastic during growth on media with different carbon sources appeared to be specific carbon‐source. In fed batch fermentation, R. etli R13 resulted in cell dry weight 6.2 g/L and PHB 51.4%. Gas chromatography‐mass spectrometry and gel permeation chromatography analysis revealed that PHB produced from R. etli R13 was solely composed of 3‐hydroxybutyric acid and the molecular mass of the purified PHB was 3.4 × 105 Da with polydispersity 1.47. Dielectric relaxation of PHB has been studied in the temperature and frequency ranges 300–440 K and 10 kHz–4 MHz, respectively. A clear dielectric α and ρ‐relaxation processes are observed in these studied ranges of temperature and frequency. The first process is due to the dipole relaxation in the crystalline phase of PHB. The second one is due to the space‐charge formation or Maxwell‐Wagner‐polarization. The α‐relaxation process has been investigated by semiempirical Havriliak‐Negami relaxation function. The activation energy (Ea) and the relaxation time (τ0) are calculated using the Arrhenius equation. The dielectric relaxation strength (Δε) is strongly temperature dependent. The calculated values of Ea for ac conductivity, ln(σ), of PHB provide information about the presence of electronic conduction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

9.
The dielectric properties of a diglycidyl ether of bisphenol A (DGEBA) epoxy resin and n‐butylamine have been studied in the frequency range 100 Hz to 3 GHz at 25 °C. The unreacted mixture showed a single relaxation which gradually split in two relaxations, the separation of which increased as the reaction progressed. The low and high frequency relaxations are attributed to the structural dynamics of the growing macromolecules and to the motions of the dipoles associated with the monomers, respectively. The increase of the structural relaxation time is described by a phenomenological relationship, similar to the Williams–Landel–Ferry equation, that allows estimation of the conversion at vitrification. A marked decrease of the electrical conductivity has also been observed, as a result of the increasing viscosity of the system. The conductivity and the structural relaxation time are correlated by means of a generalized Debye–Stokes–Einstein model. It has also been found that both components of the complex dielectric permittivity, measured at microwave frequencies, yield information on the advancement of the polymerization process. © 2001 Society of Chemical Industry  相似文献   

10.
Novel single‐ion‐conductor polymer (SCP) electrolytes based on oxalate‐chelated‐borate‐structure‐grafted poly(vinyl formal) (PVFM) were synthesized via a solution casting technique. The influence of the molar ratio of ? OH and boron atoms in PVFM on the ionic conductivity (σ) of the SCP electrolytes at different temperatures was investigated with alternating‐current impedance spectroscopy in the frequency range of 0.01 Hz to 1 MHz. The results show that σ of the SCP electrolytes at 15–60 °C was about 10?6–10?5 S/cm, and temperature dependence of the conductivity of the electrolytes followed the Vogel–Tamman–Fulcher relationship. The dielectric behaviors of the SCP electrolytes were analyzed in view of the dielectric permittivity and dielectric modulus of the electrolytes. Dielectric analysis revealed that the transport of Li+ ions in the PVFM‐based SCP electrolytes mainly followed a hopping mechanism coupled with the segmental motion of the polymer chain. Additionally, a dielectric relaxation was found in the high‐frequency region; this was a thermally activated result and also implied the appearance of carrier hopping. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43510.  相似文献   

11.
The dielectric relaxation behavior of different conducting carbon black‐filled ethylene‐octene copolymer (EOC) vulcanizates prepared by melt‐mixing method has been studied as a function of frequency (100 Hz–5 MHz) over a wide range of temperatures (25–100°C). The effect of filler loading and frequency on AC conductivity, dielectric permittivity, impedance, and dielectric loss tangent (tanδ) has been studied. The nature of variation of the dielectric permittivity with the filler loadings was explained on the basis of interfacial polarization of the filler in the polymer matrix. The effect of filler loading on the real and complex part of the impedance was explained by the relaxation dynamics of the polymer chains in the vicinity of the fillers. The effect of filler and temperature on dielectric loss tangent, dielectric permittivity, AC conductivity, and Nyquist plot was also reported. The bound rubber (BR) value increases with increase in filler loading suggesting the formation of strong interphase, which is correlated with dielectric loss. Thermal activation energy (Ea) was found to be decreasing with the temperature, which follows the Arrhenius relation: τb = τ0 exp(−Ea/KBT) where τb is the relaxation time for the bulk material. From the plot of lnτb versus inverse of absolute temperature (1/T), the activation energies (Ea) were found to be 0.37 and 0.44eV, respectively. The percolation threshold was observed with 40 phr carbon black loading. POLYM. COMPOS., 37:342–352, 2016. © 2014 Society of Plastics Engineers  相似文献   

12.
Dielectric behaviour of poly(propylene glycol) (PPG) of number‐average molecular weight 2000 g mol?1 and binary mixtures of PPG with water (PPG–W) of various concentrations were carried out in the frequency range 10 MHz to 4 GHz at 25 °C. The dielectric dispersion and absorption curves related to the orientational motion of these molecules in the binary mixtures are described by a single relaxation time using Debye's model. The values of static dielectric constant εo, high frequency limiting dielectric constant ε, and dielectric relaxation time τo were determined for PPG and PPG–W mixtures. The values of the dielectric parameters were used to explore the nature of homogeneous and heterogeneous dynamic networks formed through hydrogen bonding in the binary mixtures of PPG and water molecules with concentration variation. The dielectric studies of PPG molecules were also carried out in the same frequency range at four temperatures, namely 25, 35, 45 and 55 °C. The temperature‐dependent relaxation times were used to evaluate the thermodynamical parameters for the dielectric relaxation processes. The dielectric relaxation free energy of activation ΔFτ for PPG molecules was found in the range ~4.5 to 4.7 kcal mol?1, which corresponds to the activation energy needed for the breakage of hydrogen bonds. Furthermore, the large negative value of the entropy ΔSτ of PPG molecules confirms that the configuration involved in dipolar orientation has an activated state, which is more ordered than in the normal state. Copyright © 2004 Society of Chemical Industry  相似文献   

13.
The molecular dynamics and miscibility of highly interacting binary polymer blends of poly(methyl methacrylate) (PMMA) and poly[styrene‐co‐(maleic anhydride)] random copolymer with 8 wt% maleic anhydride content (SMA) were investigated as a function of composition over a wide range of frequency (10?2–106 Hz) at different constant temperatures (30–160 °C). Only one common glass relaxation process (α‐process) was detected for all measured blends, and its dynamics and broadness were found to be composition dependent. The existence of only one common α‐relaxation process located at a temperature range between those of the pure polymer components indicated the miscibility of the two polymer components over the entire range of composition. The miscibility was also confirmed by measuring the glass transition temperatures of the blends, Tg, using differential scanning calorimetry. The composition dependence of Tg of the blends showed a positive deviation from the linear mixing rule and well described by the Gordon–Taylor–Kwei equation. The relaxation spectrum of the blends was resolved into α‐ and β‐relaxation processes using the Havriliake–Negami (HN) equation and ionic conductivity. The dielectric relaxation parameters obtained from HN analysis, such as broadness of relaxation processes, maximum frequency, fmax, and dielectric strength, Δ? (for the α‐ and β‐relaxation processes), were found to be blend composition dependent. The kinetics of the α‐relaxation process of the blends were well described by the Meander model, while an Arrhenius‐type equation was used to evaluate the molecular dynamics of the β‐relaxation process. Blending of PMMA and SMA was found to have a considerable effect on the kinetics and broadness of the β‐relaxation process of PMMA, indicating that the strong interaction and miscibility between the two polymer components could effectively change the local environment of each component in the blend. © 2013 Society of Chemical Industry  相似文献   

14.
The polymer nanocomposite films (PNC) with varying amounts of organically modified sodium montmorillonite (DMMT) clay in poly(methyl methacrylate) (PMMA) based polymer matrix were prepared by solution cast technique. Dielectric measurements were carried out on these films as a function of frequency at 30°C and 100°C. The addition of clay significantly improved the ionic conductivity. Transport parameters, such as the diffusion coefficient (D), number density (n) and mobility (μ) of charge carriers were determined using a new approach, which is based on impedance spectroscopy. The temperature‐dependent dc conductivity, relaxation and mobility plots obey the Arrhenius rule. The results suggest that the higher ionic conductivity of these PNC films at elevated temperature is not only due to increased mobility of ions, but it is accompanied by a significant increase in carrier concentration. Analysis of DSC thermogram reveals a very high percentage of amorphous content for all samples. A good correlation among dielectric permittivity, carrier concentration, mobility and ionic conductivity has also been observed. POLYM. ENG. SCI., 58:220–227, 2018. © 2017 Society of Plastics Engineers  相似文献   

15.
In this study, reduced graphene oxide (RGO) has been introduced as conductive filler within polyaniline (PAni) nanotubes (PAniNTs) by in situ chemical reduction method to enhance the properties of PAniNTs. The effect of varied concentration of in situ reduced GO on the structural, thermal, electrical, and dielectric properties of RGO–PAniNTs nanocomposites have been investigated by high resolution transmission electron microscope, X‐ray diffraction, Fourier transform infrared, thermogravimetric analysis, IV characteristics, and impedance analyzer. The enhanced thermal stability of the nanocomposites has been analyzed from the derivative thermogravimetric curves in terms of onset and rapid decomposition temperature. The transport mechanisms have been studied by fitting the nonlinear IV characteristics to the Kaiser model. The dielectric relaxation phenomena have been investigated by permittivity and modulus formalisms. Characteristic relaxation frequency of RGO–PAniNTs nanocomposites shifts toward higher frequency with increasing RGO concentration indicating a distribution in conductivity relaxation. The distribution of relaxation time has been studied by fitting the imaginary modulus spectra of the nanocomposites to Bergman modified KWW function. The ac conductivity spectra are fitted to the Jonscher's power law equation and enhanced conductivity value of 1.26 × 10−3 S cm−1 is obtained for 40 wt % of RGO compared to 1.22 × 10−4 S cm−1 for PAniNTs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45883.  相似文献   

16.
By means of dielectric permittivity, electric modulus and impedance, the dielectric properties of LiF single crystals were investigated in the temperature range of 30°C–800°C and frequency range of 50 Hz–10 MHz. Two thermally activated relaxations, R1 and R2, were observed. The relaxation R1 showing activation energy around 0.8 eV was found to be related to the Li‐ion diffusion in the crystal. The relaxation R2 contains three Arrhenius segments, the low‐, mid‐, and high‐T segments, separated by boundary temperatures of 325°C and 425°C. These segments in the order of ascending temperature were found to be associated with F3, F3+ centers, F2 centers, and F centers, respectively.  相似文献   

17.
Nafion®‐117, sulfonated polysulfone (sPSF) and sulfonated polyetherketone (sPEK) are characterized using broadband dielectric spectroscopy in the frequency range of 10 MHz–100 mHz. Overall, there are 4–5 relaxation processes in these sulfonated membranes and a comparison of their spectral features allows assigning the relaxation processes. At an optimum amplitude of ~100 mVrms, all the relaxations are clearly defined as the electrode polarization is minimized. At low temperatures (?130 °C), these membranes show a broad relaxation peak in the mid‐frequency region, which quickly shifts towards the high‐frequency region as the temperature is increased to ?90 °C. This peak is observed in proton exchange membranes for the first time due to the use of low ac amplitude, and it is assigned to the relaxation of the confined water in the micro‐pores. With all the membranes, the peak associated with ? SO3H group relaxation is observed in the same frequency range at a temperature of ~?80 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44790.  相似文献   

18.
Dielectric response of conducting carbon‐black‐filled ethylene–octene copolymer microcellular foams has been investigated with variation of blowing agent and filler loading in the frequency range of 100 Hz to 5 MHz and temperature range from 30 to 100°C. With increase in blowing agent loading, the dielectric permittivity increases for both unfilled as well as carbon‐black‐filled microcellular foams. The experimental complex impedance plots were compared with model‐fitted plots obtained by taking an equivalent circuit of (CQR) (CR).The values of Rb (bulk resistance), Rgb (grain boundary resistance), bulk capacitance (Cb), and grain boundary capacitance (Cgb) at different temperatures were calculated and compared with experimental values. The relaxation time due to bulk effect (τb) has been calculated from relaxation frequency (fr). The dc conductivity (σdc) decreases with rise in temperature indicating the existence of positive temperature coefficient of resistance in the material. The activation energy (Ea) calculated from the relaxation time due to bulk effect (τb) was found to be 0.446 eV, whereas it was 0.363 eV from the dc conductivity plot in the temperature range of 30–100°C. POLYM. COMPOS., 37:3398–3410, 2016. © 2015 Society of Plastics Engineers  相似文献   

19.
The frequency dependent dielectric relaxation behavior of conductive carbon black reinforced chlorosulfonated polyethylene (CSM) vulcanizates has been studied for different filler loadings in the frequency range of 102–106 Hz over a wide range of temperatures (30–120°C). The effects of filler loadings on the dielectric permittivity (ε′), dielectric loss tangent (tan δ), impedance, and electrical conductivity were studied. The variation of the dielectric permittivity with the filler loadings was explained on the basis of interfacial polarization of the filler in the polymer matrix. The frequency dependence of ac conductivity has been investigated using percolation theory. The effect of filler loading on the complex and real parts of impedance was clearly observed, which can be explained on the basis of relaxation dynamics of polymer chains in the vicinity of fillers. The percolation threshold occurred near 30 phr of filler loading. Scanning electron microphotographs showed the agglomeration of the filler on and above these filler loadings. Additionally, the effect of temperature on dielectric loss tangent, dielectric permittivity, ac conductivity, and Nyquist plot of conductive black reinforced CSM vulcanizates has been studied. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers  相似文献   

20.
Temperature‐ and frequency‐dependent dielectric behaviour has been investigated for pristine, iodine‐doped and annealed polyetherimide (PEI) in the temperature range 303–523 K at various frequencies (120 Hz, 1 kHz, 10 kHz and 100 kHz). In pristine PEI, the rapid decrease in the dielectric constant (ε′) in the temperature range 303–373 K is governed by the Kirkwood model whereas the gradual decrease in ε′ in the temperature range 373–473 K is governed by β‐relaxation (dipolar) and αβ‐relaxation (hybrid) processes. The occurrence of these relaxations is confirmed by the appearance of tan δ loss peaks at ca 403 and 443 K, respectively, in ε″–T curves. The temperature‐independence of ε′ in the temperature range 473–523 K is mainly governed by the α‐relaxation process associated with large segmental groups. The tan δ loss peak appearing at 503 K confirms this relaxation process. In iodine‐doped samples, an overall increase in ε′ is attributed to the formation of charge‐transfer complexes in the polymer structure. The dominance of a new relaxation process due to interaction of iodine with ether linkages neutralizes the 1/T rule in the low‐temperature region. A significant decrease in ε′ in annealed samples below 393 K is due to the suppression of the dipolar relaxation process. The enhancement in ε′ above 393 K is due to the dominance of the α‐relaxation process. The shift in the high‐temperature tan δ loss peak towards higher temperature with increasing frequency shows the distributive nature of relaxation time for this relaxation process. Copyright © 2011 Society of Chemical Industry  相似文献   

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