Water‐sorption behavior of P‐phenylene diamine–based polyimide thin films

Four different p‐PDA–based polyimide thin films were prepared from their respective poly(amic acid)s through thermal imidization at 400°C: poly(p‐phenylene pyromellitimide) (PMDA‐PDA); poly(p‐phenylene biphenyltetra carboximide) (BPDA‐PDA); poly(p‐phenylene 3,3′,4,4′‐oxydiphthalimide) (ODPA‐PDA); and poly(p‐phenylene 4,4′‐hexafluoroisopropylidene diphthalimide) (6FDA‐PDA). Water‐sorption behaviors of polyimide films were gravimetrically investigated at 25°C and 22–100% relative humidity by using the modified electromicrobalance (Thin Film Diffusion Analyzer). The diffusion coefficients of water for the polyimides varies in the range of 1.6 to 10.5 × 10⁻¹⁰ cm²/s, and are in the increasing order: BPDA‐PDA < PMDA‐PDA ∼ ODPA‐PDA < 6FDA‐PDA. The water uptakes of polyimides vary from 1.46 to 5.80 wt %, and are in the increasing order: BPDA‐PDA < ODPA‐PDA < 6FDA‐PDA < PMDA‐PDA. The water‐sorption behaviors for the p‐PDA–based polyimides are closely related to the morphological structure; specifically, the diffusion coefficients in p‐PDA–based polyimide thin films are closely related to the in‐plane orientation and mean intermolecular distance, whereas the water uptakes are affected by the packing order. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1315–1323, 2000     

Preparation and characterization of thin films of the poly(p‐phenylene vinylene) semiconducting polymer

Conjugated polymers have been the subject of many studies because of their widespread applications in electronic and optoelectronic devices. Poly(p‐phenylene vinylene) is a leading semiconducting polymer in optical applications. This work is focused on the development of thin films of poly(p‐phenylene vinylene) by spin coating and their characterization with Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy to understand their changes. An empirical model has been developed to show the effect of the variables—the spin speed, polymer concentration, and spin time—on the film thickness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Shear flow behaviors of poly(p‐phenylene benzobisoxazole) spinning dope

In this study, the shear flow properties of Poly(p‐phenylene benzobisoxazole) (PBO)/poly(phosphoric acid) (PPA) spinning dope were studied by means of capillary rheometer. The effect of shear stress, temperature, PBO concentration, and PBO molecular weight on the apparent viscosity of PBO/PPA dope was discussed. The results showed that the apparent viscosity of the dope decreased with the increase of the shear stress and the temperature. The flow behavior index increased with the increase of temperature, which indicated that the non‐Newtonian behavior of the dope became weaker at high temperature. Moreover, it was also found that at high shear stress, the apparent viscosity of the dope was insensitive to the temperature, PBO molecular weight, and PBO concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Dynamic mechanical properties of polyimide/poly(silsesquioxane)‐like hybrid films

Polyimide/poly(silsesquioxane)‐like (PI/PSSQ‐like) films have three‐dimensional structure with linear PI blocks and a crosslinked PSSQ‐like structure. They have higher thermal stability and char yields than pure PI from 4,4′‐diaminodiphenyl ether and 3, 3′‐oxydiphthalic anhydride (ODPA). In a series of X‐PIS [PI modified with p‐aminophenyltrimethoxysilane (APTS), where X is the molecular weight of each PI block] hybrid films, decreasing the PI block chain length enhances the storage modulus, tensile modulus, and glass‐transition temperature (T_g) but reduces the α‐relaxation damping peak intensity, density, and elongation. The change in the former three properties may be caused by an increase in the crosslinking density and rigidity of the network structure. The changes in the next two properties are caused by an increase in the free volume or the PI interblock separation and decreases in the interblock PI chain interaction. The change in the last property (i.e., a decrease in elongation) is related to the increase in the rigidity of the network structure. The activation energy of the α transition depends on the chain length of the PI block. A maximum value is reached at the chain length of 10,000 because of two different factors: crosslinking density and free volume. In a series of X‐PIS‐y‐PTS [X‐PIS modified with phenyltrimethoxysilane (PTS), where y is the weight‐ratio percentage of PTS to APTS–polyamic acid] films with a constant PI block length, the storage modulus, tensile modulus, T_g, density, and α‐relaxation damping peak intensity decrease with the PTS content. This could be because of the increase of the PSSQ‐like domain size with the PTS content, which leads to the introduction of more free volume or interblock separation and to a decrease in the interblock chain interaction force. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2500–2516, 2001     

Polymeric coatings for photostability enhancement of poly(p‐phenylene vinylene) derivative films

Poly(p‐phenylene vinylene) (PPV) derivatives are an important class of conjugated polymers, known for their applications as electroluminescent materials for light‐emitting devices and sensors. These derivatives are highly susceptible to photodegradation by the combined action of oxygen and light. Here, the use of various commercial polymers as protective coatings against the photodegradation of PPV derivatives was explored. Cast films of two similar PPV derivatives, poly[(2‐methoxy‐5‐n‐hexyloxy)‐p‐phenylene vinylene] and poly[2‐methoxy‐5‐(2‐ethylhexyloxy)‐p‐phenylene vinylene], were submitted to photodegradation by exposure to white light under atmospheric conditions in order to verify if the type of side chain (linear or branched) had an effect on the photodegradation. No significant differences in the photodegradation behaviour between the two polymers were noticed. The following commercial polymers were tested as protective coatings for the PPV derivative cast films: 99 and 80% hydrolysed poly(vinyl alcohol) (PVA) and starch. The best results were achieved using coatings of 99% hydrolysed PVA, which increased about 700 times the time necessary for complete degradation of the PPV derivative films. The results show the effectiveness of this coating in minimizing and, possibly, controlling the effects of the photodegradation of PPV derivative films, which can be useful in many applications, e.g. oxygen sensors. Copyright © 2009 Society of Chemical Industry     

Studies on molecular transport of n‐alkanes through poly(tetrafluoroethylene‐co‐propylene) elastomeric membrane

Molecular transport of a series of n‐alkanes through commercial TFE elastomer (FA 150L) has been studied in the temperature range 30–50 °C using sorption‐gravimetric method. The Fickian diffusion equation was used to calculate the diffusion coefficients, which were dependent on the size of the alkanes and temperature. The diffusion coefficients at 30°C varied from 4.53 × 10^?8 cm²/s (n‐heptane) to 0.18 × 10^?8 cm²/s (n‐hexadecane). The liquid concentration profiles have also been computed using analytical solution of Fick's equation with the appropriate initial and boundary conditions and these were presented as a function of penetration depth of molecular migration and time of immersion. These results have been discussed in terms of molecular size of alkanes as well as temperature. In all the liquid penetrants, the transport phenomenon was found to follow the anomalous behavior. From the temperature dependence of diffusion and permeation coefficients, the Arrhenius activation parameters have been estimated. These parameters do not exhibit any systematic variation with the size of the penetrants. The resulting low diffusion coefficients, contribute to the superior barrier performance of the membrane, is due, in part, to the high glass transition temperature of Aflas? TFE elastomer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2228–2235, 2006     

Water sorption behaviors of the BPDA‐based polyimide films depending upon the structural isomers of diamine

For the biphenyltetracarboxylic dianhydride (BPDA)‐based polyimide thin films, the water sorption behaviors were gravimetrically investigated by using a thin film diffusion analyzer. The water sorption behaviors of the polyimide thin films are quite different and strongly dependent upon the sort of polyimide. The diffusion coefficients of the polyimide thin films vary in the range of 1.6 × 10⁻¹⁰ to 12.4 × 10⁻¹⁰cm²/s and the water uptakes vary from 1.52 to 5.25 wt %. Both the diffusion coefficient and water uptake of the polyimide thin films are in the increasing order: BPDA‐pPDA < BPDA‐p,p′ODA < BPDA‐p,m′ODA < BPDA‐mPDA ∼ BPDA‐p,p′DDS < BPDA‐m,m′DDS. Specifically, the polyimide films with para‐oriented linkages in backbone structure showed relatively lower diffusion coefficient and water uptake than the corresponding polyimide films with meta‐oriented linkages because of the well‐developed crystalline structure and good intermolecular chain ordering. In addition, the polyimide thin films having higher chain order showed relatively lower diffusion coefficient and water uptake. The crystallinity and intermolecular chain ordering in the morphological structure are critical parameters in controlling the water sorption behaviors of the polyimide thin films. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2121–2127, 2001     

Study on photoaging of poly(p‐phenylene benzobisoxazole) fiber

As a kind of rig‐rod‐like polymer, poly(p‐phenylene benzobisoxazole) (PBO) has received great interest because of its excellent mechanical properties and good thermal stability. The use of PBO fibers, however, is limited due to its low sunlight stability. In this work, the photoaging of PBO fibers, as well as the effects of oxygen and moisture on their photoaging, is investigated by tensile strength measurements, infrared spectroscopy, molecular mass determination, and scanning electron microscopy. It is first time to find that the photoaging of PBO fibers includes two development stages. The physical aging is the dominate factor at the first stage of photoaging relative to the second stage, in which the chemical aging is the dominate factor. In the first degradation stage, long defects appear and develop parallel to the fiber axis. Little chemical change occurs in this stage. In the second degradation stage, the molecular mass of PBO decreases and chemical degradation occurs. Oxygen accelerates the occurrence of chemical degradation. It is also found PBO fibers are more stable for photoaging when moisture and oxygen are isolated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The evolution of structure and properties of poly(p‐phenylene terephthalamide) during the hydrothermal aging

The evolution of structure and properties of poly(p‐phenylene terephthalamide) (PPTA) with different hydrothermal aging temperatures were systematically investigated. The cooperative change in tensile strength and reduced viscosity upon aging time indicated a direct chemical structure‐property correlation. The linear relationship between tensile strength and reduced viscosity was explored. Wide angle X‐ray diffraction measurements disclosed the crystal structure of aramid fibers was stable with aging time and temperature. Fiber exhibited skin and core structure in different ways. Cracks and microfilbrils were observed in the core after hydrothermal aging, while the structure was unchanged in the skin. Fourier transform infrared spectroscopy also proved that the chemical structure of the skin was not affected by degradation. The results elucidated the hydrolysis of amide function happened in amorphous or bundles between microfibrils in the core rather than in skin of the fiber. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fabrication of poly(lactic acid) films with resveratrol and the diffusion of resveratrol into ethanol

Poly(94% L ‐lactic acid) (PLA) films containing 0, 1, and 3 wt % resveratrol (PR0, PR1, and PR3) were extruded in a pilot‐plant scale blown‐extrusion machine. Yellow‐colored PLA films with reduced crystallinity were obtained, and the films absorbed UV‐visible light at 350–200 nm. The diffusion kinetics of resveratrol into ethanol at 9, 23, 33, and 43°C displayed Fick's behavior, and diffusion coefficients between 10⁻¹³ and 10⁻¹⁰ cm²/s were obtained. According to the Arrhenius equation, the energy of activation for the diffusion of resveratrol from PR1 and PR3 films was 175 and 177 kJ/mol, respectively. The temperature of diffusion had a stronger effect on the reduction of the weight average molecular weight of PLA than the processing conditions and the contact time with ethanol. However, diffusion of resveratrol was not affected by the degradation of PLA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Kinetics of thermal degradation of poly(p‐phenylene benzobisoxazole)

The kinetics of thermal degradation of poly (p-phenylen benzobisoxazole) (PBO) were studied by thermogravimetric analysis (TG) in dynamic nitrogen gas at four different heating rates: 5, 10, 15, 20°C/min. The activation energy calculated by Kissinger Method was 352.19 kJ/mol, and the mean value of activation energies evaluated by Flynn-Wall-Ozawa Method was 338.32 kJ/mol. The degradation kinetic model of PBO followed the mechanism of random scission of weak bonds of PBO molecule and impact of the active groups obtained from the broken bonds, Mampel Power equation with integral form G(α) = α^3/2 and differential form . And the mathematical equation of kinetic compensation effect was ln A = 0.1365 E_a − 1.4102. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3675–3679, 2007     

Moisture diffusion properties of HFPE‐II‐52 polyimide

Moisture diffusion properties of the polyimide HFPE‐II‐52 were determined using weight gain, weight loss, and swelling experiments over a temperature range of 25–200°C. Below 100°C, diffusivity was measured using standard weight loss and weight gain methods. Above 100°C, diffusivity is found by weight loss experiments performed by placing moisture saturated samples in an oven and recording weight loss dynamically. The diffusivity of the polyimide was found to obey the Arrhenius relation over the entire range of temperature. Weight gain experiments were performed to determine the equilibrium level of moisture absorbed by the polyimide as a function of relative humidity. Swelling experiments were performed to measure swelling strain as a function of moisture absorption. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3471‐3479, 2006     

Crystallization of glass fiber‐reinforced poly(p‐phenylene sulfide) nanocomposites

Ternary composites of glass fiber‐reinforced poly(p‐phenylene sulfide) (PPS/GF) filled with nanometric calcium carbonate (nano‐CaCO₃) were prepared by means of a twin‐screw extruder. The nano‐CaCO₃ surface was treated with stearate and treated with titanate, the composites being called SI composite system and SII composite system, respectively. The crystallization and heatproof properties of the PPS/GF/nano‐CaCO₃ composites were measured using a differential scanning calorimeter, to investigate the influence of the nanometric filler content on the crystallinity. The results show that the variation of the starting crystallization temperature, crystallization temperature and crystallinity with an increase of the particle weigh fraction (?_f) of SI composite system is different from that of SII composite system. When ?_f is less than 4 wt%, the crystallinity of the two composite systems increases and then decreases slightly with increasing ?_f. Moreover, the crystallization behavior and mechanisms are discussed. Copyright © 2011 Society of Chemical Industry     

Bending-beam study of water sorption by thin poly(methyl methacrylate) films

A bending-beam technique has been employed to study the effects of film thickness (7–55 μm) and rate of cooling during film preparation (～ 6°C/h to a dry ice quench) on sorption characteristics of water by poly(methyl methacrylate) films coated on thin fused quartz beams (? 84 μm thick). In each experiment, the curvature of a polymer coated beam exposed to liquid water was monitored as a function of time by a low power laser pointer. With the use of a transport model which considers the sorption process as the linear superposition of contributions from Fickian diffusion and a first-order polymer molecular relaxation process, the beam curvature data were analyzed to determine the governing transport kinetics and associated transport parameters such as water diffusion coefficient and relaxation rate constant. From curvature analysis for thin films (7–13 μm in thickness), it was found that water diffusion proceeds at early times in a Fickian-like manner with a diffusion constant of 2–4 × 10^?9 cm²/s. At later times, significant relaxation contributions lead to non-Fickian diffusion behavior, an effect that is more pronounced as the film thickness or sample cooling rate decreases. In addition, sorption of water was found to reduce the film stress (initially tensile at ? 10⁸ dyn/cm²) at a rate that increases with sample cooling rate. The high initial film stress not present in free-standing films may account for the relatively higher diffusion coefficient (～ 2 × 10^?8 cm²/s) found here for very thick (55 μm) PMMA coatings. Because the bending-beam technique uses coated samples, it is especially well suited for studying penetrant transport into polymer coatings.     

Electrical properties of poly(p‐phenylene vinylene) films with an incorporation of platinum metal nanoparticles

The effects of platinum metal nanoparticles on a conjugated polymer were investigated by monitoring the electronic structures and measuring the electrical properties of poly(p‐phenylene vinylene) (PPV) and PPV/Pt nanocomposites films. Enhanced current density in PPV/Pt nanocomposite films was obtained by the incorporation of Pt nanoparticles into the conjugated polymer PPV. This result agrees well with our observation of an increase in the electron affinity and an increase in roughness with increasing Pt nanoparticle content. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Water sorption and diffusion behaviors in composite films of poly(ether imide) and bismaleimide

The effect of a crosslinkable imide moiety, bismaleimide (BMI), on the water sorption properties of poly(ether imide) (PEl) was gravimetrically measured and interpreted together with the chemical and morphological structures in composite films. The morphological structure of composite films was investigated by using a prism coupler and X‐ray diffraction pattern. It indicated that the in‐plane orientation and intermolecular packing order increased as the content of BMI in composite films increased. The water sorption behaviors showed dependence on the morphological change originating from the addition of BMI to PEI. The composite film with relatively high content of BMI exhibited a relatively high degree of in‐plane orientation and a small mean intermolecular distance, which resulted in a decrease in the diffusion rate and water sorption and an increase in the activation energy in composite films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1692–1697, 2006     

Hydrophobic and tribological behaviors of a poly(p‐phenylene benzobisoxazole) fabric composite reinforced with nano‐TiO2

1H,1H,2H,2H‐Perfluorooctyl trichlorosilane (PFTS) was used to modify TiO₂ nanoparticles, and hydrophobic PFTS–TiO₂ nanoparticles were obtained by an ultrasonic reaction method. The PFTS–TiO₂ surface morphological and hydrophobic properties were analyzed with scanning electron microscopy (SEM), Fourier transform infrared spectrometry, and contact angle (CA) testing. Then, the poly(p‐phenylene benzobisoxazole) fabric–phenolic composite filled with PFTS–TiO₂ as a lubricant additive was fabricated by a dip‐coating process. The tribological properties of the composite were investigated, and the wear surface morphology was observed by SEM. The experimental results show that the water CA of the composite filled with PFTS–TiO₂ was 158°, and the composite containing 4 wt % PFTS–TiO₂ exhibited excellent antifriction and abrasion resistance. The hydrophobic surface of the composite showed excellent durable performance with a static water CA of 126.7° after abrasion. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45077.     

Synthesis,characterization, and ligating behavior of poly[N,N‐p‐phenylene bisacryl (methacryl)amide]

Monomers of diacylated amine were synthesized by the reaction of acryloyl chloride or methacryloyl chloride with p‐phenylenediamine. Heating DMF solution of these monomers at 75°C in the presence of AIBN as an initiator gave the corresponding polymer. The solid metallopolymer complexes with different metal salts were isolated either by the in situ addition of the monomer, metal salt, and initiator at 75°C or by the reaction of the isolated polymer with the metal salt at 150°C. The monomers, polymers, and their metallopolymer compounds were characterized using elemental analysis, IR, NMR (¹H and ¹³C), and MS spectral measurements in addition to thermal analysis. The IR data showed that the coordinating atoms of the polymer are dependent on the reaction temperature. The ion selectivity of the isolated polymers toward different metal ions either for a single metal ion or in a mixture as aqueous solutions are studied by the batch techniques. Energy dispersive spectroscopy (EDS) measurements showed that both polymers are more selective to Hg²⁺ and Pb²⁺. The morphology of the polymers and their metallopolymer complexes at different temperature was also studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2412–2422, 2006     

Ultraviolet resistance modification of poly(p‐phenylene‐1,3,4‐oxadiazole) and poly(p‐phenylene terephthalamide) fibers with polyhedral oligomeric silsesquioxane

Octa‐ammonium chloride salt of polyhedral oligomeric silsesquioxane (POSS) was synthesized by a hydrolysis reaction and introduced into poly(p‐phenylene‐1,3,4‐oxadiazole) (p‐POD) and poly(p‐phenylene terephthalamide) (PPTA) fibers by a finishing method to enhance the UV resistance. The effects of the POSS concentration, treatment temperature, and time on the tensile strength of the fibers were investigated. The surface morphology, mechanical properties, crystallinity, degree of orientation of fibers, and intrinsic viscosity of the polymer solution were characterized in detail. The results indicate that the tensile strength retention and intrinsic viscosity retention of the fibers treated with POSS were much higher than those of the untreated fibers after the same accelerated irradiation time; this demonstrated that this treatment method was feasible. We also found that the efficacy of the protection provided by POSS was more beneficial to p‐POD than PPTA because of the different structure. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42643.