Structural and dielectric properties of POSS reinforced polyimide nanocomposites

In this study, a series of [3-(2-aminoethyl)amino]propyl-heptaisobutyl substituted polyhedral oligomeric silsesquioxane (AHIP) containing polyimide (PI) nanocomposites were successfully prepared. Structural, thermal and electrical properties of the polyimide nanocomposites were studied. The properties of AHIP containing polyimides were compared with those of the neat polyimide films. The surface morphology of the prepared AHIP containing polyimides were determined by using Scanning Electron Microscopy (SEM). The hydrophilic/hydrophobic nature of AHIP/polyimide composites were analyzed by measuring their water contact angles. It was found that the addition of AHIP into the polyimide slightly increased the contact angle values. The incorporation of 5% AHIP to the PI matrix decreased the dielectric constant value of pure PI from 8.6 to 11.7, respectively. Furthermore he dielectric permittivity was changed from 8.6 (neat polyimide) to 5.5 (PI3).     

Synthesis and characterization of fluorine functionalized graphene oxide dispersed quinoline-based polyimide composites having low-k and UV shielding properties

Polyimide nanocomposites having low-k and UV shielding properties have been developed using fluorine functionalized graphene oxide and bis(quinoline amine) based polyimide. The polyimide was synthesized using bis(quinoline amine) and pyromellitic dianhydride at appropriate experimental conditions, and its molecular structure was confirmed through various spectral analysis such as FTIR and NMR. The polyimide (PI) composites were prepared using bis(quinoline amine), pyromellitic dianhydride, and separately filled with 1, 5, 10 wt% of fluorinated graphene oxide (FGO) through in situ polymerization. The polymer composites were characterized using thermo gravimetric analysis (TGA), X-ray powder diffraction (XRD), and scanning electron microscopy (SEM). In addition, the water contact angle, dielectric behavior, and UV–Vis shielding behavior of FGO/PI composites were evaluated. The value of the water contact angle of the polyimide was increased with increment of FGO in the polyimide matrix. The highest water contact angle of polyimide composites observed 108° was obtained for 15 wt% FGO reinforced polyimide composite. The value of the dielectric constant for neat, 1, 5, and 15 wt% FGO reinforced polyimide composites was obtained as 4.5, 3.7, 2.6, and 2.0, respectively. It is also observed from by UV–Vis spectroscopy analysis that the FGO reinforced polyimide composites have good UV shielding behavior.     

Industrial cutting waste granite dust reinforced cardanol benzoxazine/epoxy resin hybrid composites for high-voltage electrical insulation applications

An attempt has been made to develop hybrid composites from benzoxazine monomer (C-ddm) hybridized with DGEBA epoxy resin (EP) and reinforced with varying weight percentages (20 wt%, 40 wt%, 60 wt%, 80 wt% and 100 wt%) of glycidoxypropyltrimethoxy- silane (GPTMS) functionalized granite dust (GD) obtained from industrial granite cutting and polishing process in order to utilize them for electrical insulation applications. The thermal stability of granite dust reinforced poly(EP-co-C-ddm) composites was studied by TGA analysis. Among the composites samples studied, 100 wt% GD reinforced poly(EP-co-C-ddm) composites possess better thermal stability than that of other neat matrices and composites. Among the composites prepared using varying weight percentages of functionalized GD reinforcement, it was observed that 80 wt% GD reinforced poly(EP-co-C-ddm) composites possesses better hydrophobic character than that of other neat matrices and composites. The value of LOI calculated for neat matrix (poly[EP-co-C-ddm]) and 20 wt%, 40 wt%, 60 wt%, 80 wt% and 100 wt% GD reinforced composites was found to be 22, 28, 34, 40, 43 and 45 respectively. The 80 wt% GD reinforced poly(EP-co-C-ddm) composites possess the higher values of tensile strength and flexural strength of 47 MPa and 140 MPa, respectively than those of their samples. The values of electrical surface resistivity and electrical volume resistivity of all the neat matrices and GD reinforced polybenzoxazine composites were found to be in the order of 10¹² and 10¹³ respectively. The values of dielectric strength obtained from break down voltage (BDV) for neat matrix [poly(EP-co-C-ddm)] and 20 wt%, 40 wt%, 60 wt%, 80 wt% and 100 wt% of GD reinforced poly(EP-co-C-ddm) composites are 15.0, 15.5, 16.5, 17.0, 17.0 and 17.0 kV/mm, respectively. Data obtained from thermal stability, hydrophobic behavior and dielectric studies it was inferred that the hybrid polymer composites developed in the present work can be conveniently used in the form insulators, sealants, adhesives and matrices where application demands at high-performance industrial and engineering applications.     

Influence of aspect ratio of carbon nanotubes on crystalline phases and dielectric properties of poly(vinylidene fluoride)

Poly(vinylidene fluoride) (PVDF)-multiwalled carbon nanotube (MWNT) composites with different aspect ratios of MWNT were prepared by a coagulation method. Field emission scanning electron and transmission electron microscopic studies reveal that MWNT are well dispersed in the PVDF matrix. The X-ray diffraction and differential scanning calorimeter data indicate that the composites with high aspect ratio of MWNT have the β phase structure at the MWNT loading level of 2.0wt%, and have a mixture of α and β phase below 2wt% MWNT, and that those composites with low aspect ratio of MWNT, however, always have a mixture of α and β phase for MWNT concentrations ?2.0wt%. The dielectric constant values increase with the increase in MWNT loading level and the percent increase in dielectric constant is much greater in the composite filled with high aspect ratio of MWNT than in that loaded with low aspect ratio. And also, it has been found that the dielectric loss of the composites with MWNT loading level ?2.0wt% is still as low as neat PVDF, which is of significance for dielectric application.     

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.     

Investigation of the electrical properties of XLPE/SiC nanocomposites

The interface between nanoparticles and the polymer matrix, which dominates the electrical properties of nanocomposites, can effectively improve the DC breakdown and suppress space charge accumulation in nanocomposites. To research the interface characteristics, XLPE/SiC nanocomposites with concentrations of 1 wt%, 3 wt% and 5 wt% were prepared. The DC breakdown, dielectric properties and space charge behavior were examined using pulsed electro-acoustic (PEA) equipment and a dielectric analyzer. The test results show that the nanocomposites with concentrations of 1 wt% and 3 wt% have higher DC breakdown field strength than neat XLPE. In contrast, there is a lower DC breakdown strength at a concentration of 5 wt%, possibly due to the agglomeration of nanoparticles. Nanoparticle doping increases the real and imaginary permittivities over those of neat XLPE. Furthermore, with increasing concentration, a larger increase in the permittivity amplitude was observed. Based on the space charge behavior, all nanocomposites could suppress space charge accumulation, but the nanocomposite with a concentration of 1 wt% exhibited the best effect. Meanwhile, heterocharge accumulation near electrodes was observed in neat XLPE and the nanocomposite with a concentration of 5 wt%. In contrast, homocharge accumulation near electrodes was observed in the nanocomposite with a concentration of 3 wt%. This phenomenon may be due to different amounts of shallow traps in nanocomposites with different concentrations, which might lead to differing electron or hole mobility.     

Optical and electrical properties of copper alumina nanoparticles reinforced chlorinated polyethylene composites for optoelectronic devices

The incorporation of transition metal oxide fillers into the polymer matrix through solution mixing polymerization imparts enhanced electrical and thermal properties. The present work focused on the optical properties, crystallinity, thermal stability, temperature-dependent conductivity, dielectric constant and modulus of chlorinated polyethylene/copper alumina (CPE/Cu–Al₂O₃) nanocomposites. Optical absorption measured using an ultraviolet–visible (UV–visible) spectrometer shows enhanced intensity and a blue shift for CPE/Cu–Al₂O₃ nanocomposites. The bandgap energy of CPE/Cu–Al₂O₃ nanocomposites was lower than pure CPE and minimum bandgap energy was recorded for a 7 wt% composites. The X-ray diffraction demonstrates that Cu–Al₂O₃ nanoparticles were uniformly introduced into the CPE matrix. Thermogravimetric analysis (TGA) manifests improved thermal stability of nanocomposites. Dielectric properties decrease with frequency, whereas AC conductivity increases with frequency, and both AC conductivity and dielectric properties increase with temperature. The maximum AC conductivity and dielectric constant were obtained for 7 wt % nanofiller loaded sample. For all systems, the activation energy for electrical conductivity decreases with rising temperatures. The experimental dielectric constant values of CPE nanocomposites were correlated with different theoretical models. The Bruggeman model was in good agreement with the experimental permittivity. The impedance experiments showed a decreasing trend with temperature, indicating the semiconducting nature of prepared nanocomposites.     

Preparation of Low-dielectric Permittivity Polyimide Resins with High Surface Activity from Chemically Bonded Hyperbranched Polysiloxane

Thermosetting resin matrix is the key component of advanced wave-transparent composites,where low dielectric constant,excellent processability,high thermal stability,as well as good bonding ability are required for resins.Herein,we prepared a series of phenylethynyl terminated polyimide(PI)resins by grafting amine-functionalized hyperbranched polysiloxane(HBPSi)to PI chains during the in situ polymerization.The effects of HBPSi on the processability of oligomers,molecular packing,thermal stability,dielectric property and bonding ability to reinforce Kevlar fibers of the cured PI/HBPSi composite resins have been examined in detail.The dielectric constants of the cured composite resins were greatly reduced from 3.29 to 2.19 without compromising its processability and thermal stability.Meanwhile,the 10 wt％HBPSi-containing PI resin demonstrated better bonding ability to reinforce fibers with the interfacial shear strength(IFSS)of 37.64 MPa,compared with that of neat PI-6 matrix(27.34 MPa),and better adhesion to metal with the lap shear strength of 10.48 MPa,50％higher than that of neat resin PI-6(6.98 MPa).These resultant PI/HBPSi composite resins exhibit excellent comprehensive properties,indicating their great potential as low-dielectric constant resin matrix in radar radome.     

Preparation and dielectric properties of polyimide/silica nanocomposite films prepared from sol–gel and blending process

Using poly(amic acid) (PAA) as a precursor followed by thermal imidization, the polyimide/silica nanocomposite films were prepared via an improved sol–gel process and a blending process, respectively. FT‐IR, TEM and TGA measurements were used to characterize the structure and properties of the obtained films. The results confirmed that the introduction of silica did not yield negative effects on the conversion of the PAA precursor to the polyimide. With the increase of silica content, the aggregation of silica appeared in the polyimide matrix, and the thermal stability decreased slightly for both kinds of films. The dielectric constant (ε) of both films increased slowly with the increase of the silica concentration. The dielectric constant of the obtained polyimide/silica nanocomposite films displayed good stability within a wide range of temperatures or frequency. Based on modeling relation between ε and silica content, the difference in dielectric properties for two kinds of nanocomposites are discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

Microwave‐assisted synthesis of nanocomposites from polyimides chemically cross‐linked with functionalized carbon nanotubes for aerospace applications

Polymer‐carbon nanotube nanocomposites are extensively investigated for microelectronics and aerospace applications. In this study, novel polyimide/f‐MWCNT nanocomposites made from 2,4‐bis(4‐aminophenylamido)‐6‐chloroquinazoline, pyromellitic dianhydride and functionalized‐Multi Walled Carbon Nanotubes (f‐MWCNT) by an efficient microwave assisted method were investigated. The structure of the prepared diamine monomer was confirmed by FT‐IR, ¹H‐NMR, and ¹³C‐NMR spectral techniques. The prepared nanocomposites (T_g values from 338°C to 375°C) show improved thermal property as indicated by differential scanning calorimetry and thermogravimetric analysis. Polyimide/f‐MWCNT nanocomposites were found to have higher dielectric constant, and the limiting oxygen index values of prepared nanocomposites are in the range of 29.5 to 35.5, indicating a high flame retardancy. Additionally, the morphological studies were conducted by X‐ray diffraction and scanning electron microscopy. Overall, it is observed that chemically connected polyimide‐functionalized carbon nanotube nanocomposites could be used for aerospace and microelectronics applications that require high T_g, dielectric constant and high flame retardancy.     

Cyanate ester tethered POSS/BACY nanocomposites for low‐k dielectrics

Low‐k dielectrics have been developed as an interlayer insulating material in the large scale integrated circuitry devices by the copolymerization of various weight percentages (10, 20, 30, and 40 wt%) of cyanate ester tethered POSS (POSS‐OCN) and bisphenol‐A cyanate ester (BACY) to obtain BACY/POSS‐OCN nanocomposites. The reinforcement of POSS‐OCN significantly contributes to the reduction in the value of dielectric constant and dielectric loss as well, which might be due to the presence of porous structured POSS‐OCN. The 30 wt% POSS‐OCN/BACY nanocomposite possesses the lowest value of dielectric constant of 1.81 at 1 MHz. Copyright © 2016 John Wiley & Sons, Ltd.     

Thermal behavior of cardanol resin reinforced 20 mm long untreated bagasse fiber composites

Recently the attention in composite materials reinforced with natural fibers has significantly increased due to the new environmental legislation as well as consumer pressure that forced manufacturing industries to search substitutes for the conventional materials, e.g., glass fibers. In this way, the objective of the paper was to evaluate the thermal properties of sugarcane bagasse fiber-cardanol resin composites. Fibers were cut down to 20?mm length in diagonally. These fibers were mixed with the cardanol and epoxy resin, and fabricate in a biocomposites with different compositions, such as 0, 5, 10, 15, and 20?wt%. The thermal properties were evaluated by thermal gravimetric analysis and differential thermogravimetry analysis and also chemical formulation studied in Fourier transform infrared spectroscopy. The results showed the improved thermal strength of the composites in comparison to the neat polymer (0?wt%).     

New poly(ether-imide)/MWCNT nanocomposite

New polyimide (PI) nanocomposites containing two different amounts of MWCNT (PI/MWCNT) were prepared via in situ polymerization technique. Transmission electron microscopy showed that MWCNT was exfoliated in the polymer matrix, resulting in well-dispersed morphologies at 1 and 3 mass% MWCNT contents. The effects of multiwalled carbon nanotubes (MWCNT) on the thermal and flammability properties of new PI derived from 1,3-bis[4,4′-aminophenoxy]propane and biphenyl dianhydride were investigated by thermogravimetric analysis (TG) in nitrogen and air atmosphere, differential scanning calorimetry, and microscale combustion calorimeter (MCC). The PI/MWCNT nanocomposites were electrically conductive with maximum conductivity obtained at 3 mass% MWCNT, which is favorable for many potential applications. TG results showed that the addition of MWCNT resulted in a substantial increase of the thermal stability and char yields of the nanocomposites compared to those of the neat PI. Flame retardancy of the nanocomposites was significantly improved in the presence of MWCNT.     

聚酰亚胺/蒙脱土纳米复合材料

利用插层法合成的聚酰亚胺／蒙脱土纳米复合材料相比于纯聚酰亚胺有更好的力学性能、热稳定性、气体阻隔性及更低的介电性、吸湿性和热膨胀性。是一种性能优异、具有广泛应用前途的新型有机、无机－纳米复合材料。这是因为粘土在聚酰亚胺基体中以纳米尺度均匀分散并与基体形成了强的化学结合。本文重点综述了该复合材料的制备、结构表征及性能等方面的研究，并展望该材料的应用前景。     

Ferrocene Containing Polyimides as a Route to Low-κ Dielectric Materials

Polyimides incorporating the ferrocene unit were prepared by in situ curing of poly (amic acid) macromolecules with ferrocene, for the molecular-level design of low dielectric constant (low-κ) materials. The effects of ferrocene on dielectric properties of polyimide are investigated in detail in this study. Ferrocene containing polyimides exhibit a number of desirable properties including low-water absorption and admirable thermal stability. Systematic studies demonstrate that proper insertion of ferrocene into a polyimide backbone can give rise to a reduction in the material's dielectric constant. All composites were subjected to DSC measurements for the purpose of examining Tg from all composition. Scanning electron microscopy (SEM), X-ray diffraction (XRD) and the other conventional techniques were used for structural characterization.     

Preparation and characterization of polyimide/mesoporous silica hybrid nanocomposites based on water-soluble poly(amic acid) ammonium salt

Recently, mesoporous silica was blended with polyimide to develop low dielectric constant (k) materials with improving mechanical and thermal properties of polyimide by utilizing both the nanoporous structure and silica framework. However, even the use of mesoporous silica did not show a significant decrease of k due to the phase segregation in between polyimide and the mesoporous silica materials. In this work, we attempted to prepare polyimide/mesoporous silica hybrid nanocomposites having relatively good phase mixing behavior by utilizing polyimide synthesized from a water soluble poly(amic acid) ammonium salt, which lead to low k up to 2.45. The thermal properties of polyimide were improved by adding mesoporous silicas. For this work, we have fabricated mesoporous silicas through surfactant-templated condensation of tetraethyl orthosilicate (TEOS). Pyromellitic dianhydride (PMDA)-4,4′-oxydianiline (ODA) polyimide was prepared from poly(amic acid) ammonium salt, which had been obtained by incorporating triethylamine (TEA) into PMDA-ODA poly(amic acid) in dimethylacetamide (DMAc), followed by thermal imidization.     

Influence of heat treatment on electromagnetic properties of polyimide/carbon black composites

A kind of absorbing materials was prepared by hot pressing method using polyimide as matrix and carbon black (CB) as filler. The mechanical properties, the electromagnetic properties, and the thermal stability of polyimide/CB composites were studied. The results showed that the complex permittivity increased from 6.82 + 1.38i to 18.69 + 9.47i, whereas the flexural strength decreased from 108 MPa to 77 MPa, respectively, when the CB content increased from 2 wt% to 8 wt%. The reflection loss curves shifted to low frequency with increase of the thickness at the same content. The reflection loss below ?10 dB could be obtained in the X band with 6 wt% CB content and did not display significant difference before and after the heat treatment at 400°C for 5 h. When the content of CB was 8 wt%, the decomposition temperature (at 5% weight loss) increased approximately 42°C compared with pure polyimide matrix. Copyright © 2014 John Wiley & Sons, Ltd.     

Photosensitive fluorinated polyimides with a low dielectric constant based on reaction development patterning

The fluorinated polyimide PI(6FDA/HFBAPP) was prepared by the reaction of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA) with 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane (HFBAPP) in 1‐methyl‐2‐pyrrolidone/toluene. A multiblock copolyimide with both fluorinated and rigid‐rod segments, PI(6FDA/HFBAPP)(BPDA/2‐DMB), was prepared by the addition of a second dianhydride, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), and a second diamine, 2,2′‐dimethylbenzidine (2‐DMB), to the polyimide main chain. The potential lithographic performance of photosensitive polyimides composed of nonphotosensitive fluorine‐containing polyimides and photosensitive diazonaphthoquinone (DNQ) was studied on the basis of a new imaging principle recently proposed by our laboratory, that is, reaction development patterning. Neat PI(6FDA/HFBAPP) showed a low dielectric constant (?) of 2.41 and a low dissipation factor (tan δ) of 0.0027 at 20 GHz, and a 10‐μm resolution of the fluorinated polyimide/DNQ system was demonstrated with reactive development with a solution including ethanolamine after ultraviolet exposure. Although slight changes in the dielectric properties were observed in the presence of DNQ residues, these values (? = 2.63 and tan δ = 0.0033 at 20 GHz) were low enough for use in microelectronic applications. However, PI(6FDA/HFBAPP)(BPDA/2‐DMB), having a lower coefficient of thermal expansion (CTE; 33 ppm/°C) than PI(6FDA/HFBAPP) (49 ppm/°C), exhibited good positive photosensitivity, whereas the relatively low‐CTE multiblock copolyimide displayed a much higher ? value (3.48 at 1 MHz) than the highly fluorinated polyimide (2.88 at 1 MHz). A film consisting of PI(6FDA/HFBAPP)(BPDA/2‐DMB) and the remaining DNQ derivatives showed a CTE value comparable to that of the neat polyimide film. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 861–871, 2003     

Molecular Dynamics and Structure of Poly(Methyl Methacrylate) Chains Grafted from Barium Titanate Nanoparticles

Core−shell nanocomposites comprising barium titanate, BaTiO₃ (BTO), and poly(methyl methacrylate) (PMMA) chains grafted from its surface with varied grafting densities were prepared. BTO nanocrystals are high-k inorganic materials, and the obtained nanocomposites exhibit enhanced dielectric permittivity, as compared to neat PMMA, and a relatively low level of loss tangent in a wide range of frequencies. The impact of the molecular dynamics, structure, and interactions of the BTO surface on the polymer chains was investigated. The nanocomposites were characterized by broadband dielectric and vibrational spectroscopies (IR and Raman), transmission electron microscopy, differential scanning calorimetry, and nuclear magnetic resonance. The presence of ceramic nanoparticles in core–shell composites slowed down the segmental dynamic of PMMA chains, increased glass transition temperature, and concurrently increased the thermal stability of the organic part. It was also evidenced that, in addition to segmental dynamics, local β relaxation was affected. The grafting density influenced the self-organization and interactions within the PMMA phase, affecting the organization on a smaller size scale of polymeric chains. This was explained by the interaction of the exposed surface of nanoparticles with polymer chains.     

Fabrication of thermoplastic polyurethane composites with a high dielectric constant and thermal conductivity using a hybrid filler of CNT@BaTiO3

Thermoplastic polyurethane composites with an excellent dielectric constant and high thermal conductivity were obtained using CNT@BaTiO₃ as a filler through a low-speed melt extrusion method. Before preparing the hybrid filler for the composite, the filler particles were surface modified to ensure that the outer surfaces could facilitate the reaction among particles to form the hybrid and ensure complete dispersion in the thermoplastic polyurethane matrix. After confirming the proper surface treatment of the filler particles using infrared spectroscopy, thermal degradation analysis and field emission scanning electron microscopy, they were used to prepare the composite materials at a processing temperature of 200 °C. The thermal stability, thermomechanical properties, mechanical properties, thermal conductivity, and dielectric properties of the composites were investigated. Compared to the neat thermoplastic polyurethane matrix, the prepared composite exhibited a higher thermal stability, approximately 300% higher storage modulus, higher tensile strength and elongation at break values, approximately three times higher thermal conductivity (improved from 0.19 W/(m.K) to 0.38 W/(m.K), and approximately five times larger dielectric constant at high frequencies (at 1 MHz a dielectric constant of 19.2 was obtained).