Synergistic enhancement of mechanical,crystalline and dielectric properties of polyarylene ether nitrile‐based nanocomposites by unidirectional hot stretching–quenching

Copper tetra‐amine phthalocyanine (NH₂‐CuPc) was grafted onto barium titanate (BaTiO₃) whose surface was modified by carboxylic polyarylene ether nitrile (CPEN) to afford a nano‐filler (CPEN‐f‐BaTiO₃@NH₂‐CuPc). Through a solution‐casting method combined with ultrasonic dispersion technology, the obtained CPEN‐f‐BaTiO₃@NH₂‐CuPc was successfully incorporated into biphenyl polyarylene ether nitrile (BP‐PEN) matrix to prepare nanocomposite films with various mass fractions of CPEN‐f‐BaTiO₃@NH₂‐CuPc (0, 2.0, 5.0, 10.0 and 20.0 wt%). After that, the nanocomposite films were unidirectionally stretched with various stretching ratios at 280 °C. All the nanocomposite films show excellent mechanical and thermal stability, which is provided by the BP‐PEN matrix. The crystallinity and mechanical, thermal and dielectric properties of the nanocomposite films are efficiently enhanced after the unidirectional hot‐stretching process. The results show that hot‐stretching is a useful method for improving the mechanical and crystallization behaviors as well as the thermal and dielectric properties of the nanocomposite films. © 2017 Society of Chemical Industry     

Effect of interfacial chemistry on the linear rheology and thermal stability of poly(arylene ether nitrile) nanocomposite films filled with various functionalized graphite nanoplates

Poly(arylene ether nitrile) (PEN) nanocomposites filled with functionalized graphite nanoplates (GNs) were prepared by a simple solution‐ casting method and then characterized by rheometer and thermogravimetric analysis (TGA). This study investigates how the surface treatment of GNs affects the GN dispersion state. The linear rheological test indicated that the 4‐aminophenoxyphthalonitrile‐grafted GN (GN‐CN) presented better dispersion in PEN matrix than purified GN because the corresponding composite showed the lower rheological percolation threshold, which was further confirmed by scanning electron microscopy and solution experiments. The TGA revealed that the presence of 4‐aminophenoxyphthalonitrile‐grafted GN retarded the depolymerization evidently compared with that of purified GN, showing remarkable increase in the temperatures corresponding to a weight loss of 5 wt % (increased by 21°C) and maximum rate of decomposition (increased by 9°C). Both the dispersion state and the surface functionalization of GN are very important to the thermal stability of PEN matrix. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effects of graphene nanosheets on the dielectric,mechanical, thermal properties,and rheological behaviors of poly(arylene ether nitriles)

Poly(arylene ether nitriles) (PEN) containing various contents of graphene nanosheets (GNs) was prepared via solution‐casting method and investigated for their dielectric, mechanical, thermal, and rheological properties. For PEN/GNs nanocomposite with 5 wt % GNs, the dielectric constant was increased to 9.0 compared with that of neat PEN (3.1) and dielectric losses of all nanocomposites were in the range of 0.019–0.023 at 1 kHz. The tensile modulus and strength were increased about 6 and 14% with 0.5% GNs, respectively. The fracture surfaces of the all PEN/GNs nanocomposites revealed that GNs had good adhesion to PEN matrix. The thermal properties of the nanocomposites showed significant increase with increasing GN loading. For 5 wt % GNs‐reinforced PEN nanocomposite, the temperatures corresponding to a weight loss of 5 wt % (T_d5%) and 30 wt % (T_d30%) increased by about 20 and 13°C, respectively. Rheological properties of the PEN nanocomposites showed a sudden change with the GN fraction and the percolation threshold was about 1 wt % of GNs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of phenolphthalein/bisphenol A-based poly(arylene ether nitrile) copolymers: Preparation and properties of films

Poly(arylene ether nitrile) (PEN) is a class of high-performance engineering plastics of poly(arylene ether) with cyano groups as side groups, which can get improved thermal, mechanical, and electrical properties through simple molecular structure design. In this work, a series of PEN (BPA/PP based PEN) copolymers were synthesized with varying amounts of phenolphthalein and bisphenol A. The influence of the copolymer molecular structure variations on the thermal, mechanical, and dielectric properties of PEN copolymer films was investigated. The results demonstrated that the BPA/PP based PEN copolymer films have great mechanical properties and low dielectric constant, as well as enhanced thermal properties. The highest 5% weight loss temperature of 494.9°C was obtained by PEN-B7P3, while the highest glass transition temperature of 238.6°C was obtained by PEN-B3P7. Porous BPA/PP based PEN films prepared by non-solvent induced phase separation (NIPS) exhibited satisfactory mechanical properties and the highest tensile strength of 9.4 MPa was achieved. Moreover, the introduction of the phenolphthalein structure into the PEN molecular chain can improve the heat resistance of the PEN copolymers without deteriorating the dielectric properties, which gives the copolymers great potential as candidates for applications in flexible electronics and wireless communication.     

Effect of curing behaviors on the properties of poly(arylene ether nitrile) end-capped with phthalonitrile

Poly(arylene ether nitrile) (PEN) end-capped with phthalonitrile (PEN-n) was synthesized by incorporating phthalonitrile into the terminals of PEN. The as-prepared flexible PEN-n (after elevated temperature treatment) was characterized by infrared spectroscopy, nuclear magnetic resonance, gel permeation chromatography, and rheological measurements. In addition, the effects of curing behaviors on properties of PEN-n films were studied by thermal, dielectric and mechanical measurements. Differential scanning calorimetry analysis showed that glass transition temperature of PEN-n was improved from 176 to 232°C as the curing temperature and time increased. Thermal gravimetric analysis revealed that initial decomposition temperature of PEN-n cured at 320°C for 2 h was 570°C. Mechanical properties showed that tensile strength of PEN-n uncured and cured at 320°C for 3 h was 85 and 97 MPa, respectively. The dielectric properties showed that the dielectric constant of PEN-n film decreased from 4.0 to 3.1 as the curing time increased and dielectric loss of PEN-n was 0.01 at 100 kHz. This kind of PEN-n film may be used as a good candidate for high-performance polymeric materials. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of polybenzimidazole/functionalized carbon nanotube nanocomposite films for use as protective coatings

Functionalized multi‐walled carbon nanotubes (MWCNTs) via microwave‐induced polymerization modification route, and polybenzimidazole (PBI) nanocomposite films containing 0.1‐5 wt% functionalized MWCNTs were successfully synthesized. The functionalized MWCNTs were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and X‐ray photoelectron spectroscopy (XPS). The results verify that the polymer was successfully grafted to the MWCNTs with a polymer layer that was several nanometers thick. The TGA results showed that the quantity of the attached polymer reached approximately 9.4 wt%. The mechanical properties of the nanocomposite films were measured by tensile test and dynamic mechanical analysis (DMA). The tensile test results indicated that the Young's modulus increased by about 43.9% at 2 wt% CNT loading, and further modulus growth was observed at higher filler loading. The DMA studies indicated that the nanocomposite films had a higher storage modulus than pure PBI film in the temperature range of 30‐300°C, and the storage modulus was maintained above 0.82 GPa. Simulation results confirmed that the PBI nanocomposite films had desirable mechanical properties for use as a protective coating. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers.     

Design and properties of polyarylene ether nitrile copolymers with improved elongation at break

Polyarylene ether nitrile (PEN) based on biphenol exhibits a high glass transition temperature of 216°C, a high tensile strength of 110 MPa, and low elongation at break of approximately 4%. A series of PEN random copolymers with improved elongation at break were synthesized using various bisphenol compounds and 2,6-dichlorobenzonitrile (DCBN). The resulting PEN random copolymers exhibited a high glass transition temperature and thermal stability up to 513°C in a nitrogen atmosphere. PEN copolymers were amorphous and could easily be cast into transparent films with a tensile strength of 97.93–117.88 MPa and tensile modulus of 2187.98–2558.44 MPa. Most importantly, elongation at break of these PEN copolymers was higher than 13%. PEN copolymer films had a dielectric constant of 3.77–3.89 at 1 kHz and extremely low dielectric loss (<0.02). At the same time, the breakdown strength of PEN was in the range of 137.92–198.19 kV/mm and energy storage density was in the range of 0.32–0.68 J/cm³. Excellent mechanical, thermal, and dielectric properties of PEN make it possible to use them as high-temperature resistant dielectrics to act on high-temperature resistant insulated cables.     

Mechanical,thermal, electrical,and interfacial properties of high‐performance bisphthalonitrile/polyarylene ether nitrile/glass fiber composite laminates

Bisphthalonitrile (BAPh)/polyarylene ether nitrile end‐capped with hydroxyl groups (PEN‐OH) composite laminates reinforced with glass fiber (GF) have been fabricated in this article. The curing behaviors of BAPh/PEN‐OH prepolymers have been characterized by differential scanning calorimetry and dynamic rheological analysis. The results indicate that with the introduction of PEN‐OH the curing temperature of BAPh has decreased to 229.6–234.8°C and BAPh/PEN‐OH prepolymers exhibit large processing windows with relatively low melt viscosity. The BAPh/PEN‐OH/GF composite laminates exhibit tensile strength (272.4–456.5 MPa) and modulus (4.9–10.0 GPa), flexural strength (507.1–560.9 MPa), and flexural modulus (24.0–30.4 GPa) with high thermal (stable up to 538.3°C) and thermal stabilities (stable up to 475.5°C). The dielectric properties of BAPh/PEN‐OH/GF composite laminates have also been investigated, which had little dependence on the frequency. Meanwhile, scanning electron microscopy results show that the BAPh/PEN‐OH/GF composite laminates display excellent interfacial adhesions between the matrix and GFs. Herein, the BAPh/PEN‐OH matrix can be a good matrix for high‐performance polymeric materials and the advanced BAPh/PEN‐OH/GF composite laminates can be used under high temperature environment. POLYM. COMPOS., 34:2160–2168, 2013. © 2013 Society of Plastics Engineers     

The influence of cross‐linking reaction on the mechanical and thermal properties of polyarylene ether nitrile

The processing of cross‐linked polyarylene ether nitrile (PEN), which has a triazine rings structure, has been investigated under different reaction times and temperatures. In this study, the PEN films prepared by the tape‐casting formed the thermally stable triazine rings by catalytic cross‐linking reaction gradually, which was characterized by Fourier transform infrared spectroscopy. The chemical cross‐linking reaction occurred as the CN group absorption of PEN at 2221 cm⁻¹ decreased and a new absorption peak, at 1682 cm⁻¹, was observed, and the absorption peak intensity would be progressively larger, with the extension of the processing time. After the formation of cross‐linking networks, the cross‐linking degree and thermal and mechanical properties of the processed films were improved substantially, compared with the untreated films. The film with added ZnCl₂ as the catalyst was more rapidly cross‐linked, and its properties were better than that without catalyst at the same treatment conditions. The glass‐transition temperature (T_g) of PEN films processed at 350°C for 4 h (213.65°C) was higher than that of PEN films before the treatment (161°C), and the tensile strength was also improved significantly. The PEN was processed at 350°C for 2 h, whose initial decomposition temperature increases by about 10°C, compared with that of untreated film, at one time. The rheology behavior of the cross‐linked films was processed on dynamic rheometer to monitor and track the process of polymer cross‐linking reaction. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Viscoelasticity and thermal stability of poly(arylene ether nitrile) nanocomposites with various functionalized carbon nanotubes

Poly(arylene ether nitrile) (PEN) nanocomposites containing various functionalized multi‐walled carbon nanotubes (MWCNTs) were prepared through a solution‐casting method. The as‐prepared PEN nanocomposites were investigated using parallel‐plate rheometry and thermogravimetric analysis, aimed at examining the effect of surface functionalization on the dispersion of MWCNTs from the viscoelastic and thermal properties. The linear viscoelasticy results indicated that 4‐aminophenoxyphthalonitrile‐grafted MWCNTs presented better dispersion in the PEN matrix than purified and carboxylic MWCNTs because the corresponding composite showed the lowest rheological percolation threshold, which was further confirmed from scanning electron microscopy, dissolution experiments and solution rheological experiments. The thermogravimetric analysis results revealed that the presence of 4‐aminophenoxyphthalonitrile‐grafted and carboxylic MWCNTs retarded the depolymerization compared with purified MWCNTs, showing a marked increase in the temperature corresponding to a loss of 5 wt% (increased by 14–22 °C) and maximum rate of decomposition (increased by 4–8 °C). Both the state of dispersion and the surface functionalization of MWCNTs are very important to the thermal stability of the PEN matrix. Copyright © 2011 Society of Chemical Industry     

Synergetic effect of cyanogen functionalized carbon nanotube and graphene on the mechanical and thermal properties of poly (arylene ether nitrile)

Cyanogen functionalized carbon nanotube and graphene/poly (arylene ether nitrile) (CNT-CN/GN-CN/PEN) nanocomposite films were prepared by a facile solution casting method. The weight ratio of CNT-CN/GN-CN was varied from CNT-dominated to GN-dominated for the purpose of investigating their synergetic effects on the mechanical and thermal properties of PEN nanocomposites. Consequently, GN-CN/PEN composites demonstrated better mechanical and thermal properties than CNT-CN/PEN composites due to larger contact area between GN-CN and PEN matrix. Nevertheless, all CNT-CN/GN-CN/PEN composites exhibit enhanced mechanical properties than those of GN-only nanocomposites. With the increasing of CNT-CN/GN-CN weight ratio, the mechanical properties of CNT-CN/GN-CN/PEN composites increase, then decrease, and reach their maximums when CNT-CN/GN-CN weight ratio is around 4/4. From scanning electron microscope images, it is found that around that point GN-CN is flatly dispersed and CNT-CN is penetrated into GN-CN, capable of transferring stress load and thus decreasing interface loss. Thermal properties of CNT-CN/GN-CN/PEN composites once again confirmed the joint effect of CNT-CN and GN-CN, leading to improved thermal properties. In short, a synergistic effect between one-dimensional (1-D) CNT and two-dimensional (2-D) GN on the mechanical and thermal properties of nanocomposites have been demonstrated in these systems.     

Crystallinity of poly(arylene ether nitrile) copolymers containing hydroquinone and bisphenol A segments

The hydroquinone (HQ) and bisphenol A (BPA) type poly(arylene ether nitrile) (PEN) (HQ/BPA‐PEN) were synthesized through nucleophilic aromatic substitution polymerization from HQ, BPA, and 2,6‐dichlorobenzonitrile (DCBN). The prepared copolymers were characterized by intrinsic viscosity, Fourier transform infrared (FTIR), and dynamic rheological analysis. The properties of resultant copolymers were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and mechanical testing. The results showed that the PEN copolymers exhibited crystallization performance with excellent thermal and mechanical properties. HQ/BPA‐PEN10 was made into films by solution‐casting process and then were treated at different temperatures (200, 260, 280, 300, 310, and 320 °C) for different times (1, 2, 3, 4, and 5 h) to investigate the crystallinity. Results showed that when isothermal treatment temperature is 310 °C and isothermal treating time is 4 h, HQ/BPA‐PEN10 showed best properties. At this condition, the melting enthalpy, crystallinity, tensile strength, and elongation at break of the sample is 17.7 J/g, 14.11%, 132.9 MPa, and 6.1%, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46412.     

Effect of surface functionalization on the properties (rheological,mechanical, and dielectric) and microtopography of PEN/CPEN‐f‐CNTs nanocomposites

Novel carboxylic poly(arylene ether nitrile)s (CPEN) functionalized carbon nanotubes (CPEN‐f‐CNTs) were successfully prepared by a simple and effective solvent–thermal route. The CPEN‐f‐CNTs were subsequently used as the novel filler for preparation of high performance poly(arylene ether nitrile)s (PEN) nanocomposites. The SEM characterization of the PEN nanocomposites revealed that the CPEN‐f‐CNTs present better dispersion and interfacial compatibility in the PEN matrix, which was confirmed by the linear rheological analysis (Cole–Cole plots) as well. Consequently, the improved thermal stability (increased initial and maximum decomposition temperature) and enhanced mechanical properties (tensile strength and modulus) were obtained from nanocomposites using CPEN‐f‐CNTs. More importantly, the PEN/CPEN‐f‐CNTs nanocomposites not only show a high dielectric constant but also have low dielectric loss. For example, a dielectric constant of 39.7 and a dielectric loss of 0.076 were observed in the PEN composite with 5 wt% CPEN‐f‐CNTs loading at 100 Hz. Therefore, the flexible PEN/CPEN‐f‐CNTs nanocomposites with outstanding mechanical, thermal and dielectric properties will find wide application in the high energy density capacitors. POLYM. COMPOS., 37:2622–2631, 2016. © 2015 Society of Plastics Engineers     

Graphene nanoplatelet‐reinforced semi‐crystal poly(arylene ether nitrile) nanocomposites prepared by the twin‐screw extrusion

Graphene nanoplatelet reinforced semi‐crystal poly(arylene ether nitrile) (PEN/GN) nanocomposites were prepared by an economically and environmentally friendly method of twin‐screw extrusion technique. The feasibility of using PEN/GN nanocomposites was investigated by evaluating their thermal behaviors, mechanical, and morphological properties. Thermal studies revealed that GN could act as nucleating agents but decreased the whole crystallinity in/of PEN/GN nanocomposites. Mechanical investigation manifested that GN had both strengthening effect (increase in flexural modulus and strength) and toughening effect (rise in the elongation and impact strength) on the mechanical performance of semi‐crystal PEN nanocomposites. Heat treatment can further increase their mechanical performances due to the increased crystallinity and release of inner stress. With the small addition of GN (<5 wt%), the morphology of PEN was changed from brittle to ductile, and GN showed good dispersion and adhesion in/to the PEN matrix. This work shows that in the semi‐crystal polymer/filler systems, besides the dispersion states of fillers and interactions between fillers and polymer matrices, the crystallinity of the nanocomposites affected by the existence of filler and the residual stress are also two key factors determining the mechanical properties. POLYM. COMPOS., 35:404–411, 2014. © 2013 Society of Plastics Engineers     

Crystallized polyarylene ether nitrile blends with improved thermal,mechanical, dielectric properties,and processability

In this work, the biphenol polyarylether nitrile (BP‐PEN) films with improved processability were prepared by blending low molecular weight (LMW) with high molecular weight (HMW) of BP‐PEN. The hybrid membrane exhibited excellent thermal stability and mechanical strength. The T_id values of the films were as high as 505°C–522°C. Melting behavior studies indicated that the crystallinity of LMW BP‐PEN was higher than that of HMW, which was confirmed by the X‐ray diffraction (XRD) patterns analysis as well. Scanning electron microscope (SEM) provided additional information on morphology and phase adhesion. Additionally, the polymer crystallinity dependent on dielectric properties of blends films is reported. Most importantly, it is found that the combination of LMW and HMW BP‐PEN would be an effective method to simultaneously increase the mechanical, thermal, dielectric properties, and polymer processability. POLYM. COMPOS., 38:126–131, 2017. © 2015 Society of Plastics Engineers     

The properties (rheological,dielectric, and mechanical) and microtopography of spherical fullerene‐filled poly(arylene ether nitrile) nanocomposites

Poly (arylene ether nitrile)/fullerene (PEN/fullerene) nanocomposites were prepared by a facile solution‐cast method and the rheological, dielectric, mechanical, and morphological properties of the resulted nanocomposites were systematically studied and compared. Rheological studies showed PEN/fullerene nanocomposites percolation network formed at fullerene containing of 1.50 wt %, when the shear frequency was fixed at 0.1 Hz, the fitted rheological percolation threshold was about 1.55 wt %, very close to the experimental observations. The dielectric transaction occurs when the fullerene loading reached 1.50 wt %, that is very close to its rheological percolation threshold. At this point, PEN/fullerene nanocomposites also showed the optimal mechanical properties with a tensile strength of 93.6 MPa and modulus of 1951.5 MPa, which is increased by 27% and 15% compared with the pure PEN. SEM and TEM images have manifested the separate fullerene aggregated to fullerene bundles in PEN/fullerene nanocomposites, and the dispersion of fullerene bundles begin to go bad when the containing above 1.50 wt %. The PEN/fullerene nanocomposites can be widely used due to its excellent dielectric and mechanical performance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40100.     

Polyarylene ether nitrile/divinyl siloxane-bisbenzocyclobutene composite films: Curing reaction and thermal/mechanical/dielectric properties

Polymer dielectrics, are commonly used as insulating materials for electronic products. Light weight, good mechanical properties and high thermal conductivity are important properties. However, electrical and thermal parameters are interrelated, and it is challenging to have a dielectric polymer that is also resistant to high temperatures and high thermal conductivity. Hence, high-performance composite films were prepared by the method of post-solid phase chemical reaction using polyarylene ether nitrile (PEN) and divinyl siloxane-bisbenzocyclobutene (BCB) as raw materials. First, parameters of the curing reaction were determined by rheological and activation energy calculations. Then, through adjusting the content of BCB resin and treatment temperature, the performance of PEN/BCB composites could be tuned. Thermal properties have been studied by differential scanning calorimetry, dynamic mechanical analysis, thermal gravimetric analysis, and hot-disk method. Here, the PEN/BCB composite electric insulating materials with outstanding thermal performance (T_g: 208–400°C, T_5%: 469–544°C, thermal conductivity: 1.270–2.215 W/m K). Besides, its mechanical and dielectric properties were investigated in detail. It is noteworthy that the tensile strength of composite film can exceed a maximum of 130 MPa, which is 23.19% higher compared to the untreated one. Also, PEN/BCB composites own low dielectric constant (2.27–4.08 at 1 KHz), and the relationship between frequency or a wide temperature range and dielectric constant/loss is stable. Thus, it has a greater potential for applications in electronics in high-temperature environments.     

Different filler effect of carbon nanotube and graphene nanoplatelet in the poly(arylene ether nitrile) matrix

The different filler effects of identical nitrile‐functionalized carbon nanotubes (CNTs) and graphene nanoplatelets (GNs) in a poly(arylene ether nitrile) (PEEN) matrix were investigated. PEEN/CNT and PEEN/GN composites were prepared by a facile solution‐casting method and systematically investigated for their differences in morphological, thermal and rheological properties. In the PEEN matrix GNs contact one another in a plane‐to‐plane manner, while CNTs are separated. Compared with PEEN/CNT composites, PEEN/GN composites below 2 wt% filler content exhibited higher thermal stability. Rheological properties of the resulting composites indicated that PEEN/GN composites were more sensitive to strain and exhibited higher η*, G′ and G″ than PEEN/CNT composites. The rheological percolation for CNTs is over 2 wt%, higher than that for GNs (around 1 wt%). All these differences originate from the different dimensions and structures of CNTs and GNs: GNs with a flake‐like structure and larger surface area can have stronger physical and interfacial interactions with the polymer matrix. This work gives a comparative view of the different filler effects that functionalized CNTs and GNs can have in the polymer host. With identical processing technology, GNs can show a stronger filler effect than CNTs. © 2012 Society of Chemical Industry     

The interfacial effect of TiO2–Ag core–shell micro‐/nanowires on poly(arylene ether nitrile)

Novel TiO₂–Ag core–shell micro‐/nanowires (TiO₂ shell coating on Ag core) have been successfully prepared via a solvent–thermal method. Energy dispersive spectroscopy and X‐ray diffraction analyses revealed that the micro‐/nanowires were composed of Ag, Ti and O elements, and Ag was face‐centered cubic whereas TiO₂ was mainly amorphous. Interestingly, scanning electron microscopy (SEM) and transmission electron microscopy results showed that most of the TiO₂ bristles were perpendicular to and uniformly studded on the surface of the Ag cores. Subsequently, TiO₂–Ag/poly(arylene ether nitrile) (PEN) composite films were prepared via a solution‐casting method in order to investigate the effect of TiO₂–Ag on the PEN matrix. SEM images showed that there was good interfacial adhesion between fillers and PEN matrix owing to the special bristle‐like structure. Thermal analysis results showed that the TiO₂–Ag/PEN composite films possessed excellent thermal properties endowed by the PEN matrix. The dielectric constant of the composite films increased to 9.3 at 100 Hz when the TiO₂–Ag loading reached 40 wt%. Rheology measurements revealed that the network formed by TiO₂–Ag was sensitive to shear stress and nearly time independent. © 2013 Society of Chemical Industry     

Effect of nonsolvent on the structures and properties of poly(arylene ether nitrile) films prepared by the phase inversion method

In this study, a series of nonsolvents including ethyl acetate (EAC), acetic acid (HAC), n-butyl alcohol (NBA), iso-propyl alcohol (IPA) and ethanol (EA) were selected during the phase inversion process of poly(arylene ether nitrile) (PEN) films. The mechanism of film formation was tightly related with the interactions among polymer, solvent and nonsolvent. In the case of EAC, the aggregated sphere in P-EAC confirmed the in situ aggregate mechanism of polymer chains during the phase inversion process. As the nonsolvent-polymer interaction increases from HAC, NBA, IPA to EA, the phase inversion mechanism was gradually changed from the delayed to transient, as verified by the morphology transformation from spongy-like to finger-like. Dielectric, mechanical properties of these PEN films are tightly related with the morphological features, while their thermal properties are similar. Among them, P-EAC show the optimal properties for potential application in the low-k films, with a dielectric constant, T_d5%, tensile strength of 1.99, 515.84°C, and 36.08 MPa, respectively. This work can provide references for tailoring the structures and properties of PEN films through rational selection of nonsolvent via the phase inversion method.