Preparation, characterization and dielectric properties of 4,4-diphenylmethane diisocyanate (MDI) based cross-linked polyimide films

Four different types of cross-linked polyimides based on 4,4-diphenylmethane diisocyanate (MDI) were prepared by the reaction of different types of conventional poly(amic acid) intermediates with MDI as a cross-linking agent. Subsequently, they were thermally imidized in order to obtain corresponding cross-linked polyimide structure. The results of FTIR-ATR showed that MDI can effectively react with carboxylic acid groups of PAA to form cross-linked polyimide films. TGA, FTIR-ATR and SEM analyses were carried out for characterization of cross-linked polyimide (CPI) films. Moreover, the electrical properties such as dielectric breakdown strength, dielectric constant, I-V characteristics and loss factor of MDI based cross-linked polyimides have been checked. In addition, some physical properties such as water uptake, adhesion, hardness and solubility properties of the films were investigated.The results showed that all CPI films have good insulating properties such as high dielectric breakdown voltage, low loss factor (tan δ), leakage density and excellent physical properties.     

高介电常数石墨烯/聚酰亚胺复合材料的制备与性能

在原位聚合制备氧化石墨烯/聚酰亚胺复合材料的过程中,加入季铵盐表面活性剂,抑制氧化石墨烯在高温亚胺化时的聚集,同时将氧化石墨烯原位还原,获得高介电常数的石墨烯/聚酰亚胺复合材料.结果表明,采用四丁基溴化铵和四丁基碘化铵作为还原剂,利用原位化学还原方法所制备的石墨烯/聚酰亚胺复合材料的介电常数超过聚酰亚胺薄膜40倍以上,复合材料的热稳定性和机械性能也优于聚酰亚胺薄膜.热重分析结果表明,在复合材料高温亚胺化过程中,季铵盐发生热分解,未残留在复合材料中.     

Fluorinated polyimide/POSS hybrid polymers with high solubility and low dielectric constant

A series of fluorinated polyimide/POSS hybrid polymers(FPI-4-FPI-16) were prepared via a facile synthetic route using 2,2'-bis(trifluoromethyl)benzidine, 4,4'-oxydiphthalic dianhydride and monofunctional POSS as starting materials. The hybrid polymers showed excellent solubility and film formation ability. Flexible and robust hybrid films could be conveniently obtained via solution-casting. The hybrid films demonstrated low dielectric constants and high thermal stability. Their dielectric constants were in the range of 2.47–2.92 at 1 MHz measured for their capacitance, and were tunable and decreased with an increase of POSS content. Their 10% weight loss temperatures were in the range of 539-591 ℃ and the weight residual at 800 ℃ ranged from 48% to 53% in nitrogen atmosphere. These hybrid films also possessed good mechanical properties and hydrophobic characteristics. This work could provide a potential strategy for the preparation of fluorinated polyimide/POSS hybrid polymers.     

Mechanical properties degradation of polyimide films irradiated by atomic oxygen

Mechanical properties of polyimide films are degraded by exposure to a low earth orbit environment. The main environmental factor for that degradation is atomic oxygen (AO). Using tensile tests, AO-irradiated surface topography observations, and fracture surface analyses, this study investigated the degradation behavior of polyimide films’ mechanical properties by increased AO fluence and its accompanying degradation mechanisms. Tensile strength and elongation of polyimide films were reduced concomitantly with increased AO fluence. Furthermore, AO-irradiated polyimide films fractured from the AO-irradiated surfaces, of which roughness became marked as AO fluence increased. These results reflect that reduction of mechanical properties is attributable to the roughness increase in AO-irradiated surfaces. Polyimide films coated with indium tin oxide (ITO) were also evaluated to confirm the degradation behavior of AO protective films. Surfaces of ITO-coated polyimide films remained smooth even after AO irradiation. However, undercut cavities were formed at ITO coating defect sites. Rupture of ITO-coated polyimide films initiates from the undercut cavities, engendering large reduction of tensile strength and elongation. The degradation of the mechanical properties of ITO-coated polyimide films increased substantially until the undercut cavities fully penetrated the film.     

Conductivity measurement and dielectric,impedance and modulus spectroscopic studies on bis (P-nitrophenol) melaminium monohydrate

The present work is aimed to study the dielectric and electrical characteristics of bis (P-nitrophenol) melaminium monohydrate (BNPM) over the temperature and frequency ranges of 333–453 K and 50 Hz–5 MHz, respectively. The dielectric properties such as dielectric constant (ε′), dielectric loss (ε″), ac-conductivity (σ_ac), real (M′) and imaginary part (M″) of dielectric modulus were investigated as a function of temperature and frequency. The impedance analysis has been carried out using Cole-Cole plots to elucidate the electrical conduction mechanism. Further, observations indicated that the grain boundaries are more resistive and capacitive than the grains, inducing inhomogeneity in the material, which, in turn, causes broad frequency-dependent dielectric anomalies. The observed frequency-dependence of the AC conductivity validated the Jonscher power law. Further, an asymmetric dispersion peak in the imaginary part of the electrical modulus (M”) was noticed, indicating that the fabricated material exhibits non-Debye relaxation behavior.     

Novel soluble thermally stable silane-containing aromatic polyimides with reduced dielectric constant

Bis(p-aminophenoxy)diphenylsilane (BPS), bis(m-aminophenoxy)diphenylsilane (BMS) and bis(5-amino-1-naphthoxy)diphenylsilane (BAS) as three silane-diamines were prepared by the reactions of 4-aminophenol, 3-aminophenol, and 5-amino-1-naphthol respectively, with dichlorodiphenylsilane in the presence of triethylamine. The related silane-containing polyimides were prepared by two-step polycondensation reactions of these diamines with three different aromatic dianhydrides. All the polymers were characterized and their physical and thermal properties were studied. The polymers showed high thermal stability while their solubility was greatly increased in polar aprotic solvents. Wide angle X-ray diffraction showed that all the polyimides were almost amorphous. Also their dielectric constants were decreased due to the incorporation of softening and low-polarizing siloxane units into the polymer backbone.     

Synthesis,characterization, optical,thermal and electrical properties of polybenzimidazoles

The variation of dielectric constant and dielectric loss of two novel polybenzimidazole (PBI) were studied at constant temperature with variable frequency. The polymers have shown maximum dielectric constant at low applied frequency 50 Hz at 393 K due to the space charge polarization. The AC conductivity and activation energy of polymers were arrived from dielectric constant and dielectric loss values. PBIs were synthesized by the oxidative polycondensation of benzimidazole monomers, 2-(1H-benzo [d] imidazole-2-yl)-4-bromophenol (BIBP), and 2-(1H-benzo [d] imidazole-2-yl)-6-methoxyphenol (BIMP) in an aqueous alkaline medium using NaOCl as oxidant. The monomers and polymers were characterized by various spectroscopic techniques. Fluorescence spectra of monomers and polymers showed their λ _max emission in the region of 472–479 and 463–472 nm respectively. The electrical conductivities of iodine doped polybenzimidazoles were measured by four-point probe technique and it increases with increase in iodine vapour contact time. The electrical conductivity values were correlated with the charge density on imidazole nitrogen obtained from Huckel calculation method. Both the PBI are having reasonably good thermal stability and are shown by high carbines residues of around 40% at 500°C in thermogravimetric analysis.     

Dielectric behavior of polyaniline synthesized by different techniques

Polyaniline doped with dodecylbenzenesulfonic acid (Pani.DBSA) was synthesized by different procedures: by a dedoping-redoping process, by one step inverted emulsion polymerization and by one step aqueous dispersion polymerization. The effect of these different techniques on the electric properties (dielectric constant, dielectric losses, and complex electric modulus) of the corresponding emeraldine base has been studied by thermal dielectric analyzer (DETA) in the temperature range −130 °C to 200 °C and in frequency range 0.03-10⁵ Hz. It was found that the preparation technique has significant influence on the dielectric properties of Pani. The different synthetic routes give rise to polyaniline with different distribution of electric relaxation process, indicating different chain structure. Emeraldine base from Pani.DBSA prepared by one step aqueous dispersion polymerization exhibits one single relaxation peak with narrow distribution whereas that prepared by inverted emulsion polymerization exhibits two relaxation peaks, indicating two-phase structure as indicated by a bimodal distribution of relaxation process. Emeraldine base from Pani.DBSA prepared by dedoping-redoping process presents an intermediary behavior. Percentage crystallinity of Pani.DBSA samples has also been investigated using wide-angle X-ray diffraction analysis. Pani.DBSA prepared by aqueous dispersion exhibited higher crystallinity degree, which agrees with the higher conductivity.     

Synthesis of a new aromatic dianhydride monomer and related polyimide

A novel aromatic dianhydride monomer,3,3′-oxybis[(3,4-dicarboxyphenoxy)phenol]dianhydride,was successfully synthe- sized in three steps using 3,3′-oxybis(phenol)as starting material,which was reacted with 4,4′-oxydianiline(ODA)via a conventional thermal or chemical imidization method to produce a new polyimide.The resulting polyimide exhibited excellent solubility,and film-forming capability.     

Porphyrin-containing polyimide films deposited by high vacuum co-evaporation

Thin films of porphyrin-containing polyimide were produced by high vacuum co-evaporation of 4,4′-hexafluoroisopropylidene diphthalic anhydride (6FDA), 3,3′-diaminodiphenyl sulfone (DDS) and 5,10,15,20 meso-tetraphenyl porphyrin (TPP). The films were characterized by FT-IR analysis, optical absorption and emission spectroscopy. FT-IR analysis shows that the film matrix is comprised of only unreacted monomers. The conversion of monomers to polyamic acid and the following condensation to polyimide were studied by curing the samples at temperatures up to 240 °C. The amount of polyamic acid increases from room temperature to 120 °C, while at higher temperature it starts to condense to polyimide. Optical analysis shows that TPP is incorporated in the film matrix and its chemical state is determined by the interaction with the monomers, polyamic acid and polyimide. After curing the TPP molecules are finely dispersed in the polyimide matrix and their absorption and fluorescence properties are wholly preserved.     

Surface characterization of polyimide films

 Various kinds of poly(amide acid)s were prepared by the reaction of four kinds of acid dianhydride and three kinds of diamine in N,N-dimethylacetamide (DMAc). Polyimide films were prepared by casting the poly(amide acid) solution on soda glass substrates, followed by thermal imidization at various temperatures. Contact angles of polyimide films for the sides in contact both with air and with glass substrate (air side and glass side, respectively) were measured to evaluate the dispersive component (γ^D _S) and the nondispersive component (γ^P _S) of surface free energy (γ_S) of polyimide films. It was shown that, for the air side, γ^P _S value decreased greatly and γ^D _S values increased slightly with the development of imidization. Values of γ^P _S for the glass side were much higher than those for the air side. Poly(amide acid) solution was also cast on quartz glass and silicone rubber, and was thermally imidized. The γ^P _S for the quartz glass side was almost the same as that for the soda glass side. But the γ^P _S for the silicone rubber side was as low as the γ^P _S for the air side. Attenuated total reflection infrared spectroscopy of polyimide films showed that the degree of imidization for the glass side surface was not as high as that for the air side surface, and that the amount of polar groups for the glass side surface was higher than that for the air side surface. Among the various kinds of polyimides, there is a slight but clear difference in the values of γ_S and its components, which can be rationalized from the difference in the chemical structure. It was also found that thermal degradation and oxidation can be easily detected from the change of surface free energy and its components for the polyimide films after being treated at high temperatures in both air and vacuo. Received: 22 January 1998 Accepted: 10 March 1998     

Dielectric relaxation behavior of SDS/β-CD organized self-assembly in dilute aqueous solution

Dielectric relaxation behavior of SDS/β-CD self-organized with mass concentrations from 1% to 7% was investigated. The phase microstructure of SDS/β-CD aqueous solution was confirmed by analyzing the dielectric parameters. The dielectric relaxation behavior was attributed to the interfacial polarization between vesicle and medium, and the relaxation distribution parameter can indicate the shape transition from vesicles to microtubules with increasing concentration. Dielectric relaxation provided a new method to study surfactant organized self-assembly.     

Dielectric properties of plasma polymerized PVCa and composite PVCa:Au films

Dielectric properties of plasma polymerized PVCa and composite PVCa:Au films had been analyzed in the frequency range from 10 to 10⁵ Hz. In order to explain experimental data obtained the modification of Maxwell-Garnett and Bruggeman self-consistent models for the case of three-component composite has been done. The theoretical analysis performed allows to determine peculiarities of dielectric behavior of a three-component system, as well as to disclose the procedure of evaluation of third-component parameters. Results of this analysis are in agreement with experimental ones.     

Mechanical properties of BPDA-ODA polyimide fibers

An aromatic polyimide was synthesized via a one-step polycondensation reaction between biphenyltetracarboxylic dianhydride (BPDA) and 4,4′-oxydianiline (ODA) in p-chlorophenol. The polyimide (BPDA-ODA) solution dopes were spun into fibers by means of dry-jet wet spinning. The as-spun fibers were drawn and treated in heating tubes for improving the mechanical properties. The thermal treatment on the fibers resulted in a relatively high tensile strength and modulus. Thermal mechanical analysis (TMA) was employed to study the linear coefficient of thermal expansion (CTE). Thermal gravimetry analysis (TGA) spectra showed that the BPDA-ODA fibers possessed an excellent property of thermo-oxidative degradation resistance. The sonic modulus E_s of the polyimide fibers was measured.     

Effect of carbon nanotubes on mechanical and electrical properties of polyimide/carbon nanotubes nanocomposites

Multi-walled carbon nanotubes (MWNTs) reinforced polyimide nanocomposites were synthesized by in situ polymerization using 4,4′-oxydianilline, MWNTs, and pyromellitic dianhydride followed by casting, evaporation and thermal imidization. A homogeneous dispersion of chemically modified MWNTs was achieved in polyimide matrix as evidenced by scanning electron microscopy and atomic force microscopy. The incorporation of the modified MWNTs enhanced the mechanical properties of the polyimide due to the presence of strong interfacial interaction between the polymer matrix and the nanotubes in polymer composites. The resultant polyimide/MWNTs nanocomposites were electrically conductive with significant conductivity enhancement at 3 wt% MWNTs, which is favorable for many practical uses.     

Microstructure and properties of organosoluble polyimide/silica hybrid films

Organosoluble polyimide/silica hybrid materials were prepared via the sol-gel process and their pervaporation properties were studied. The organosoluble polyimide (PI) was based on 4,4′-oxydiphthlic dianhydride (ODPA) and 4,4′-diamino-3,3′-dimethyldiphenylmethane (DMMDA). The surface chemical structure of polyimide/silica films was analyzed by Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) and the results show that the completely hydrolysis of alkoxy groups of precursors and formation of the three-dimensional Si-O-Si network in the hybrid films. The morphology and the silica domain thus obtained were studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. The silica particle size in the hybrid is in the range of 40-100 nm for the hybrid films when the amount of silica is less than 20 wt%. The strength and the modulus of the hybrid films are improved and the mechanical properties were found to be strongly dependent on the density of the crosslink. The glass transition temperature (T_g) of the hybrid films was determined by dynamic mechanical analysis (DMA) and the value increased 15-20 °C as the silica content increased. Furthermore, the pervaporation performances of the prepared hybrid films were also investigated for the ethanol/water mixtures at different temperature.     

The Possible Presence of Triple Ions in Electrolyte Solutions of Low Dielectric Permittivity

The cause of the appearance of a minimum in the molar electrical conductivity in many electrolyte solutions with increasing electrolyte concentration, in solvents of low dielectric permittivity, is reviewed. Tentative explanations include the formation of triple ions or, alternatively, changes in the electrical polarization of the solutions due to the presence of electrolyte ion pairs. Theoretical models for linear triple ions and apolar dimers are examined. Experimental evidence favors the polarization hypothesis over triple ions; the presence of a maximum in the dielectric permittivity with increasing electrolyte concentration is consistent with the presence of an equilibrium between ion pairs, AB, and their dimers, A₂B₂, at higher concentrations.     

Dielectric properties of ion-exchange beads of sulfonic acid type dispersed in aqueous solutions — effect of fixed charge density

Ion-exchange beads with different densities of fixed charges were prepared by sulfoethylation of dextran gel beads. The relative permittivities and the electrical conductivities of the ion-exchange beads in a sodium form were evaluated by a dielectric technique consisting of the following two procedures proposed in a previous study (2): (a) Dielectric measurements for densely packed sediments of the ion-exchange beads; (b) Analysis of the observed dielectric relaxations by means of a theoretical equation of interfacial polarization for suspensions of spherical particles. The deduced permittivities of the ionexchange beads in equilibrium with water were about 60, which is lower than those of outer aqueous phases. The deduced conductirities were of the order of 1 to 10 mS cm^–1 and were increased reasonably with the fixed charge density. Closer consideration on these deduced values indicates that no specific interaction exists between the counter ions and the fixed charges irrespective of changes in fixed charge density and temperature.     

Dielectric properties of thermally degraded chloroprene rubber

We performed dielectric measurements on thermally aged carbon-black-filled chloroprene rubber (CR). Primary and secondary processes were observed in unaged and thermally aged CR. The primary process is due to the cooperative motion of chloroprene chains in CR, and the secondary process is due to the local motion of chloroprene chains. For the primary process, the relaxation time slightly increases and symmetric shape parameter of the loss spectrum decreases with increasing aging time. For the secondary process, the relaxation strength decreases with increasing aging time, and reaches zero after 50 h. These changes in the dielectric relaxation parameters are due to the progress of the dehydrochlorination reaction at the chloroprene chains.     

Investigation of degradation mechanisms in mechanical properties of polyimide films exposed to a low earth orbit environment

The degradation of the mechanical properties of polyimide films was evaluated by means of tensile tests after exposure to a low earth orbit (LEO) environment. Polyimide films irradiated with atomic oxygen (AO), ultraviolet (UV) light, and electron beam (EB) rays using ground simulation facilities were also evaluated similarly and compared. In these experiments tensile stress (7.0 MPa or less) was applied to the samples in order to assess its effects on mechanical properties. The mechanical properties of the flight samples decreased concomitantly with increased exposure duration. The fracture surfaces exhibited characteristic radiated patterns initiating from the exposed surfaces which showed a rough texture. In the AO-irradiated samples the mechanical properties degraded and the surface texture developed as the AO fluence increased; similar fracture surfaces appeared in the flight samples. In contrast, UV and EB irradiation had little impact on mechanical properties. Based on these results, the eroded surfaces by AO irradiation served as the starting points of the rupture, resulting in degradation of mechanical properties of polyimide films exposed to a LEO environment. The tensile stress states induced no difference in evaluations.