Colorless polyimide nanocomposite films: Thermomechanical properties,morphology, and optical transparency

Polyimide (PI)/organoclay hybrid films were prepared by the solution intercalation method, using dodecyltriphenylphosphonium‐mica (C₁₂PPh‐Mica) as the organoclay. The variations with organoclay content of the thermomechanical properties, morphology, and optical transparency of the hybrids were examined for concentrations from 0 to 1.0 wt %. For low clay contents (≤ 0.5 wt %), the clay particles are better dispersed in the matrix polymer, without the formation of large agglomerates of particles, than they are for high clay contents. However, agglomerated structures form and become denser in the PI matrix for clay contents ≥ 0.75 wt %. This is in agreement with the observed trends in the thermomechanical properties and the optical transparency, which worsen drastically when the clay content of the C₁₂PPh‐Mica/PI hybrids reaches 0.75 wt %. However, when the amount of organoclay in the hybrid is 0.75 wt %, the initial modulus of the hybrid film is at its maximum value. The PI hybrid films were found to exhibit excellent optical transparencies and to be almost colorless. It was found, however, that the transparency decreases slightly with increases in the organoclay content because of agglomeration of the clay particles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Construction of fluorenyl-modified low dielectric constant polyimide films with excellent mechanical properties and optical transparency

In order to meet the requirements of highly integrated and miniaturized electronic components, there is an urgent need for low dielectric materials with high mechanical properties and optical transparency in the field of microelectronics. In this study, a series of novel polyimide films (FPI) containing fluorenyl were prepared, and the effects of the fluorenyl content on the thermal, mechanical, and dielectric properties of the copolymerized films were investigated and discussed. The results demonstrate a significant decrease in the dielectric constant of the FPI films following the introduction of fluorenyl into polyimide (PI) chain segment. The FPI films also exhibited high mechanical properties, including tensile strengths between 92 and 106 MPa and elongation at break in the range of 8.4%–13.0%. Additionally, the introduction of the noncoplanar fluorenyl considerably improved the optical transparency and solubility of the FPI film. It is noteworthy that the FPI-3 has the best dielectric properties, with a low dielectric constant of 2.61 at 10 MHz and shows low water absorption (0.49%). The results show that we have prepared a novel low dielectric PI material film with excellent mechanical properties and optical transparency by introducing fluorenyl into the PI chain segment. These FPI films with satisfactory properties may be good candidates for dielectric materials for electronic components.     

Thermal mechanical and dynamic mechanical property of biphenyl polyimide fibers

High‐performance polyimide fibers possess many excellent properties, e.g., outstanding thermal stability and mechanical properties and excellent radiation resistant and electrical properties. However, the preparation of fibers with good mechanical properties is very difficult. In this report, a biphenyl polyimide from 3,3′,4,4′‐biphenyltetracarboxylic dianhydride and 4,4′‐oxydianiline is synthesized in p‐chlorophenol by one‐step polymerization. The solution is spun into a coagulation bath of water and alcohol via dry‐jet wet‐spinning technology. Then, the fibers are drawn in two heating tubes. Thermal gravimetric analysis, thermal mechanical analysis, and dynamic mechanical analysis (DMA) are performed to study the properties of the fibers. The results show that the fibers have a good thermal stability at a temperature of more than 400°C. The linear coefficient of thermal expansion is negative in the solid state and the glass transition temperature is about 265°C. DMA spectra indicate that the tanδ of the fibers has three transition peaks, namely, α, β, and γ transition. The α and γ transition temperature, corresponding to the end‐group motion and glass transition, respectively, extensively depends on the applied frequency, while the β transition does not. The activation energy of α and γ transition is calculated using the Arrhenius equation and is 38.7 and 853 kJ/mol, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1653–1657, 2004     

Regenerated cellulose/layered double hydroxide nanocomposite films with improved mechanical property

Construction of environment-friendly biomass-based nanocomposites with high performance is in great demand for developing of a sustainable low-carbon society. Here, transparent and flexible regenerated cellulose (RC)/layered double hydroxide (LDH) nanocomposite films were prepared from aqueous NaOH/urea solutions. The obtained nanocomposite films were characterized using AFM, SEM, FTIR, XRD, tensile testing, water contact angle, and thermogravimetric analysis. The results show that LDH nanoplatelets were individually dispersed with a thickness of 1 nm and surface diameter of 100 nm after ultrasonic treatment. Strong interaction existed between LDH nanoplatelets and cellulose molecules, leading to the improved thermal stability and mechanical strength of RC together with the original good properties of LDH. In particular, the nanocomposite films with 10 wt% LDH showed a 135% and 234% increase in the tensile strength and Young's modulus than those of the neat RC film. Meanwhile, the nanocomposite films exhibited high transparency. Therefore, these RC/LDH nanocomposites are promising in the fields of high-performance packaging materials, flexible display panels, and high-temperature dielectric materials.     

Effect of organoclay on the morphology,mechanical, and thermal properties of polyimide/organoclay nanocomposite foams

A series of polyimide (PI)/organoclay nanocomposite foams containing different contents of organoclay were prepared by the monomer in situ intercalative polymerization. The effect of organoclay on the chemical structure, morphology, mechanical, and thermal properties of the nanocomposite foams was studied. Fourier transform infrared spectra showed that the hydrogen bonds between organoclay and the polymer matrix were formed. X‐ray diffraction and transmission electron microscope results indicated that the organoclay were well dispersed in the PI matrix. The compressive strength and tensile strength of the nanocomposite foams enhanced significantly, especially for the nanocomposite foam containing 4 wt% organoclay, increasing by 15% and 9%, respectively, compared with these of the neat PI foam, and the presence of the organoclay in the PI foam improved apparently the cellular structure of the nanocomposite foams. Besides, thermogravimetric analysis revealed that the addition of organoclay improved the thermal stability of the nanocomposite foams strongly, and dynamic mechanical analysis indicated that the incorporation of organoclay significantly influenced the storage modulus of the nanocomposite foams. POLYM. COMPOS., 35:2311–2317, 2014. © 2014 Society of Plastics Engineers     

Thermal and electrical behavior of polyimide/silica hybrid thin films

Silica‐containing polyimide films were prepared by sol‐gel technique using a poly(amic acid) and tetraethoxysilane. The poly(amic acid) was synthesized by solution polycondensation reaction of 4,4′‐oxydiphthalic anhydride with 2,6‐bis(3‐aminophenoxy)benzene and an aminosilane coupling agent, 3‐aminopropyltriethoxysilane. The properties of these films, such as water vapors sorption capacity, dynamic contact angles and contact angle hysteresis, thermal, and electrical behavior have been evaluated with respect to their structure. The polymer films exhibited good thermal stability having the initial decomposition temperature above 450°C, glass transition temperature in the range of 223?228°C, and low‐dielectric constant in the range of 2.64?3.16. Two subglass transitions, γ and β, were evidenced by dynamic mechanical analysis and dielectric spectroscopy. The surface morphology and the roughness were investigated by atomic force microscopy and scanning electron microscopy. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Enhanced mechanical and anisotropic thermal conductive properties of polyimide nanocomposite films reinforced with hexagonal boron nitride nanosheets

To attain thermally conductive but electrically insulating polymer films, in this study, polyimide (PI) nanocomposite films with 1–30 wt% functionalized hexagonal boron nitride nanosheets (BNNSs) were fabricated via solution casting and following imidization. The microstructures, mechanical and thermal conductive properties of PI/BNNS nanocomposite films were examined by taking account of the relative content, anisotropic orientation, and interfacial interaction of BNNS and PI matrix. The scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and X-ray diffractometry data revealed that BNNSs with hydroxy and amino functional groups have specific molecular interactions with PI matrix and they form stacked aggregates in the nanocomposite films with high BNNS loadings of 10–30 wt%. The tensile mechanical strength/modulus, thermal degradation temperatures, and thermal conductivity of the nanocomposite films were found to be significantly enhanced with increasing the BNNS loadings. For the nanocomposite films with 1–30 wt% BNNS loadings, the in-plane thermal conductivity was measured to be 1.82–2.38 W/mK, which were much higher than the out-of-plane values of 0.35–1.14 W/mK. The significant anisotropic thermal conductivity of the nanocomposite films was found to be owing to the synergistic anisotropic orientation effects of both BNNS and PI matrix. It is noticeable that the in-plane and out-of-plane thermal conductivity values of the nanocomposite film with 30 wt% BNNS were ~1.31 and ~3.35 times higher than those of neat PI film, respectively.     

Effect of clay treatment on structure and mechanical behavior of elastomer-containing polyamide 6 nanocomposite

The effect of clay organophilization on mechanical behavior and structure of PA6/EPR blends was studied. It has been shown that the modification of clay affected simultaneously the degree of PA6 matrix reinforcement, size and structure of dispersed EPR. The localization of clay with less polar treatment in the interfacial area brought an important new effect consisting intensification of toughening effect of dispersed elastomer by formation of “core-shell” particles. Basic aspects governing formation of this advantageous structure are reported.The best balanced mechanical behavior was achieved when combining two differently modified clays, whereas the clay with less polar treatment is preblended with EPR. In this way, a high degree of matrix reinforcement (exfoliation of clay with more polar treatment) was combined with favorable size and structure of dispersed EPR phase. Additionally, at lower clay content, synergy between clay and elastomer phase, monitoring itself by enhancement of toughness, was found.     

Effects of clay orientation and aspect ratio on mechanical behavior of nylon-6 nanocomposite

The mechanical properties of nylon-6/clay nanocomposites with variations in clay aspect ratio and orientation were studied. A large-scale simple shear process was utilized to alter the clay aspect ratio and orientation within the reference nanocomposite. It was found that the modulus, strength, and heat distortion temperature of the nanocomposites decreased as the clay aspect ratio and degree of orientation were reduced. Furthermore, the reduction of clay aspect ratio and orientation led to an increase in fracture toughness and ductility. The Halpin-Tsai and Mori-Tanaka micromechanics-based models were implemented to gain a better understanding with regard to the dependence of clay structural parameters, i.e. aspect ratio and orientation, on the reinforcement effect of the nanofillers. The micromechanical models can accurately describe the relationship between clay structural parameters and the corresponding moduli for exfoliated nanocomposites.     

Carbon black thin films with tunable resistance and optical transparency

Layer-by-layer assembly was used to produce highly conductive thin films of carbon black and polymer. Positively and negatively-charged polyelectrolytes, polyethylenimine (PEI) and poly(acrylic acid) (PAA), were used to stabilize carbon black in aqueous mixtures that were then deposited onto a PET substrate. The effects of sonication and pH adjustment of deposition mixtures on the conductivity and transparency of deposited films was studied, along with drying temperature. Sonication and oven drying at 70 °C produced films with the lowest sheet resistance (∼1500 Ω/sq), which is a bulk resistivity below 0.2 Ω cm for a 14-bilayer film that is 1.3 μm thick. These two variables improve packing and connectivity amongst carbon black particles that results in increased electrical conductivity. Increasing the pH of the PAA-stabilized mixture and decreasing the pH of the PEI-stabilized mixture resulted in transparent films due to increased polymer charge density. These pH-adjusted films have much higher sheet resistance values than their non-adjusted counterparts due to their reduced thickness and patchy deposition. Varying the number of bilayers allows both sheet resistance and optical transparency to be tailored over a broad range. Carbon black-filled thin films able to achieve these levels of resistivity and transparency may find application in a variety of optoelectronic applications.     

Poly(ethylene oxide)/clay nanocomposite: Thermomechanical properties and morphology

Poly(ethylene oxide) (PEO)/clay nanocomposites were prepared by a solution intercalation method using chloroform as a solvent. The nanocomposites were characterised by X-ray diffraction (XRD), differential scanning calorimetry (DSC), hot-stage polarized optical microscopy (POM), Fourier transform infrared spectroscopy (FT-IR), tensile analysis, dynamic mechanical analysis (DMA) characterisation techniques. Formation of nanocomposite was confirmed by X-ray diffraction (XRD) analysis. A decrease in PEO crystallinity in case of nanocomposite, was confirmed by a decrease in the heat of melting and spherulite size as indicated by DSC and POM studies, respectively. Improvement in tensile properties in all respect was observed for nanocomposites with optimum clay content (12.5 wt%). DMA studies indicate an increase in loss peak temperature and broadening of loss peak as a result of clay intercalation.     

Study on morphology control and how to affect mechanical properties of polyimide/silica hybrid films

A series of polyimide (PI)/silica hybrid films were prepared by sol–gel method, using hydrolyzed tetraethoxysilane and poly amic acid‐imides (PAA‐Is), which were different imidization degree controlled by chemical imidization method. The imidization degree was characterized by Fourier transform infrared spectra and their corresponding morphology was characterized by scanning electron microscopy. The results show that there are two kinds of silica particles and their formative morphology obeys the double phase separation mechanism. According to the increase of PAA‐I imidization degree, amount of nano silica particles decreased and the diameter of macro silica particles increased in the hybrid films. Tensile testing, dynamic mechanical analysis, and thermal mechanical analysis results show that, according to the amount of nano silica particles increasing, the hybrids have the higher the mechanical properties, glass transition temperature (T_g), and thermal expansion coefficient. Through controlling PI/silica hybrid films microstructure, its mechanical properties can be controlled. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polystyrene nanocomposite materials: Preparation,morphology, and mechanical,electrical, and thermal properties

In this study, we prepared polystyrene (PS) resin nanocomposites with antistatic properties by melt‐blending PS with nanoscale zinc oxide (ZnO). The effects of nanoscale ZnO on the electrical and physical characteristics of the PS nanocomposites were investigated. Two kinds of nanoscale powders, spherical zinc oxide (s‐ZnO) and zinc oxide whisker (w‐ZnO), were selected. The coupling agents vinyltriethoxysilane (VTES) and phenyltriethoxysilane (PTES) were used to improve the compatibility between the nanopowders and PS resin. The addition of s‐ZnO and w‐ZnO improved the antistatic characteristics of the materials. The surface resistivities of the s‐ZnO and w‐ZnO nanocomposites were significantly reduced by modification with VTES and PTES. The addition of ZnO nanopowder increased the flexural modulus and reduced the flexural strength. The silane coupling agents improved the flexural properties of the nanocomposites. The glass‐transition temperatures and thermal degradation temperatures of the ZnO/PS nanocomposites increased with ZnO content. Treatment with silane increased the glass‐transition temperatures and thermal degradation temperatures of the composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2266–2273, 2005     

Structure–property correlation for thin films of semi-interpenetrating polyimide networks. I. Miscibility,curing, and morphology studies

Three different semi-interpenetrating polymer network (semi-IPN) polyimide systems were prepared through blending in solution by using 2 different polyimides, BPDA–PDA and PMDA–ODA (E), and 2 different oligomers, bismaleimide (MDAB) and phenylthynyl-terminated BPDA–PDA (BPDA–PDA–PEPA) oligomers. The oligomers are used as crosslinkers to modify the morphology of polyimides. The results show that both MDAB and PEPA are miscible with BPDA–PDA, but MDAB is immiscible with PMDA–ODA (E). Fourier transform infrared spectrum, dynamic mechanical thermal analysis data, and calculated crosslinking density indicate that there are crosslinking networks in these semi-IPN polyimide systems. In addition, the density and wide-angle X-ray diffraction results confirm that the molecular ordering and packing order are reduced by the addition of oligomers for these semi-IPN polyimide systems. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 261–272, 1998     

Effects of water on the preparation,morphology, and properties of polyimide/silica nanocomposite films prepared by sol–gel process

Polyimide/silica (PI/SiO₂) nanocomposite films with 10 wt % of silica content were prepared by sol–gel process under the conditions with and without additional water. The presence of additional water has great effect on the silica particle size and thus on the properties of the prepared PI/SiO₂ films. The results indicated that with additional water, the silica particles formed before the imidization of poly(amic acid) (PAA) and aggregated with the increasing of temperature and degree of the proceeding imidization process. For the nonaqueous process, the hydrolysis condensation reaction of tetraethoxysilane (TEOS) did not occur until the imidization of PAA took place, and no silica particles were found in the unimidized PAA films. The hydrolysis–condensation reaction of TEOS was initiated simultaneously by the trace water released from the imidization reaction, the self‐catalysis mechanism of the approach provide a means of achieving uniformly dispersed silica particles formed in the PI matrix with particle size in the range of 30–70 nm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1579–1586, 2007     

Effect of silane functionalized alumina on poly(vinyl butyral) nanocomposite films: Thermal,mechanical, and moisture barrier studies

In this work, a hybrid‐polymer nanocomposite film, based on polyvinyl butyral/amino‐silane functionalized nano alumina, was fabricated by melt processing. The calcium degradation measurements suggest the functionalized nanocomposite films exhibit higher resistance towards moisture penetration as compared to the neat alumina loaded films. Thermal stability, mechanical strength, and contact angle studies of the composites were also conducted to evaluate the performance of the functionalized alumina loaded films. These nanocomposite films were encapsulated over Al/P3HT/ITO Schottky structured device. The changes observed in the current density of the devices to the applied voltage before and after accelerated aging conditions are presented. The nanocomposite with functionalized alumina films exhibits 50% change in current density, which is superior to that attained with neat and non‐functionalized films. POLYM. COMPOS., 35:1426–1435, 2014. © 2013 Society of Plastics Engineers     

PP/clay nanocomposite: optimization of mixing conditions with respect to mechanical properties

Polypropylene/clay nanocomposites were studied with focus on optimization of mixing conditions. Two different types of commercial nanofillers Dellite^® were used (Dellite^® 72T and Dellite^® 67G). Effect of various concentrations of fillers on morphology and mechanical properties was investigated. Conditions of preparation were varied with respect to mixing time and speed of rotation of kneaders. Results of morphology study showed that nanocomposites contained agglomerates of nanofillers. The comparison of the filler types revealed that better dispersion and distribution was found for nanocomposites containing Dellite 72T which had also better tensile strength. Optimum mixing time was 30 min. 3D graphical analysis showed that the optimum speed of rotation was 60 rpm and with increasing clay content (2–10 wt%) the tensile strength increased.     

An intrinsic flame retardant epoxy resin with high transparency and strengthened mechanical property

In order to search for multifunctional epoxy thermosets (EP) with low flammability, high transparency and satisfied mechanical performance, DOPO-based phosphonate ammonium salt (DOA) was synthesized from 10-hydroxy-9,10-dihydro-9-oza-10-phosphaphenanthrene-10-oxide (DOPO-OH) and 2-amino-2-methyl-1,3-propanediol (AMPD). Under the influence of DOA, the flame-retardant and mechanical performances of the resulting EP were obviously improved. On account of the enhanced interaction and the incorporated flexible fragments in epoxy macromolecular chains, the tensile strength, elongation at break, and impact toughness of EP/5.0 wt% DOA significantly increased from 65.4 ± 1.2 MPa, 6.7 ± 0.6%, and 12.1 ± 1.3 kJ m⁻² of EP to 81.4 ± 2.8 MPa, 10.6 ± 0.5%, and 18.0 ± 1.1 kJ m⁻², respectively. In the presence of DOA, the limiting oxygen index (LOI) value of EP/5.0 wt% DOA increased to 35.5% and it passed the underwriter laboratories-94 vertical burning tests (UL-94 V) and got a V-1 rating. Moreover, the peak value of heat release rate (PHRR) was decreased by 38.0%. The analyses of char residues and volatile products showed that the activities of DOA on reducing the flammability of EP were ascribed to the protective effect of the char, the release of incombustible gases, and the radical-capture action of phosphorus-containing free radicals. Moreover, the modified epoxy thermosets still retained a high transparency.     

Thermal and thermomechanical behavior of amino functionalized and metal decorated MWCNTs/PMMA nanocomposite films

The homogeneous nanocomposites (NC) films of amino modified and metal decorated multiwall carbon nanotubes (MWCNTs) with polymethylmethacrylate (PMMA) were synthesized through in‐situ free radical polymerization. Silver metal nanohybrids (Ag/MWCNTs) were prepared by two strategies, that is, reduction of metal salt in presence of sodium dodecyl sulfate and in‐situ growth from AgNO₃ aqueous solution. The amino functionalization by ball milling enhanced the dispersion of MWCNT in monomer and produced a new class of radiation resistant NC. These synthesized films were characterized by FTIR, TGA, TEM, EDX, TC, DMA, and optical microscopy to ascertain their structural morphologies, thermal stability, and mechanical strength. Microscopic studies reflect the homogeneous mixing of amino functionalized and metal decorated MWCNTs in polymer matrix contributing in the enhancement of thermal stability, thermo‐mechanical strength, glass transition temperatures, and thermal conductivity of NC even at 0.25 wt% addition of modified nanofiller. The thermal stability of NC film at 0.25 wt% loading was increased around ≂50°C and the raise of thermo‐mechanical properties was observed up to 85% at 100°C in the presence of adsorbed surfactant. Thermal and thermomechanical behavior of pre and post UV/O₃ irradiated NC films has been compared with neat polymer. The results revealed that amino modified nanofiller embedded network in polymer matrix can effectively disperse the radiation and has a dramatic reinforcement effect on the nature of degradation of PMMA matrix. POLYM. COMPOS., 35:1807–1817, 2014. © 2013 Society of Plastics Engineers     

Tensile deformation and morphology changes in segmented elastomer films and fibers including mechanical property modeling

Segmented polyether soft segment (SS) elastomers with different hard segments (HS) in film and fiber form were studied by birefringence, DSC, and tensile tests. To understand the morphological contributions to property differences, high resolution tapping AFM resolved ribbon-like highly anisotropic hard domain (HD) lamellae in low modulus Pebax (polyamide 12 HS) and polyetherester (PEE), films, while lower HS content high melting poly(urethane urea) (PUU) had much smaller less anisotropic but higher melting HDs, explaining its enhanced thermal and mechanical hysteresis properties. Stress–strain tensile data demonstrate the excellent strength and toughness of PUUs and some spun PEE fibers, and film and fiber birefringence data applied during strain cycling up to very high stresses provided the molecular basis for the varying properties. The parameters from non-Gaussian fits of tensile data provide insight into network properties for these systems exhibiting very high strengths and a large degree of strain hardening. Modeling of PEE and Pebax films also shows the effects of substantial plastic yielding of the HD networks. Tensile data were obtained as a function of strain rate and temperature to help understand the contributions of network restructuring and other factors. For fibers, strain rate data spanning seven decades show and unusual drop in strengths at very high strain rates. Temperature-dependent tensile data also show large differences between PUU materials versus lower melting PEEs.