Ionic conductivity and morphology of semi‐interpenetrating‐type polymer electrolyte entrapping poly(siloxane‐g‐allyl cyanide)

We prepared a semi‐IPN (interpenetrating network)‐type solid polymer electrolyte (SPE) using poly (ethylene glycol)dimethacrylate (PEGDMA) as a polymer matrix containing a monocomb‐type poly(siloxane‐g‐allyl cyanide) and poly(ethylene glycol)dimethylether (PEGDME) for the lithium secondary battery. The poly(siloxane‐g‐allyl cyanide)s were prepared by a hydrosilation reaction of poly (methyl hydrosiloxane) with allyl cyanide and characterized by ¹H NMR and FTIR. The semi‐IPN‐type electrolyte was prepared by thermal curing, and conductivities of samples were measured by impedance spectroscopy using an indium tin oxide (ITO) electrode. The ionic conductivity of the semi‐IPN‐polymer electrolyte was about 1.05 × 10^?5 S cm^?1 with 60 wt % of the poly(siloxane‐g‐allyl cyanide) and 6.96 × 10^?4 S cm^?1 with 50 wt % of the PEGDME and 10 wt % of the poly(siloxane‐g‐allyl cyanide) at 30°C. The SEM morphology of the cross section of the semi‐IPN‐polymer electrolyte film was changed from discontinuous network to continuous network as increasing the PEGDME content and decreasing the poly(siloxane‐g‐allyl cyanide) content. The mechanical stability was also enhanced when increasing the PEGDME content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Electroactive characteristics of interpenetrating polymer network hydrogels composed of poly(vinyl alcohol) and poly(N‐isopropylacrylamide)

An interpenetrating polymer network (IPN) composed of poly(vinyl alcohol) (PVA) and poly(N‐isopropylacrylamide) (PNIPAAm) was prepared by the sequential IPN method. The equilibrium swelling ratio and bending behavior under electric fields of the IPN hydrogel were measured in an aqueous NaCl solution. The IPN exhibited a high equilibrium swelling ratio, in the range 280–380%. When the IPN in aqueous NaCl solution was subjected to an electric field, the IPN showed significant and quick bending toward the cathode. The IPN hydrogel also showed stepwise bending behavior, depending on the electric stimulus. In addition, the ionic conductivity of the IPN hydrogel was measured using dielectric analysis, and its conductive behavior followed the Arrhenius equation. The conductivity of the IPN hydrogel and the activation energy for the form of the IPN were 1.68 × 10^?5 S/cm at 36°C and 61.0 kJ/mol, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 890–894, 2003     

Electroconductive paper prepared by coating with blends of poly(3,4‐ethylenedioxythiophene)/poly(4‐styrenesulfonate) and organic solvents

Electroconductive papers were produced by coating commercial base papers with blends of poly(3,4‐ethylenedioxythiophene)/poly(4‐styrenesulfonate) (PEDOT:PSS) and organic solvents. The bulk conductivities of the coated papers were measured using a four‐probe technique. One‐sided and two‐sided coating gave comparable conductivity levels. The presence of sorbitol and isopropanol in the PEDOT:PSS blends did not enhance the bulk conductivity of the coated paper, and with increasing concentrations of these solvents, the conductivity decreased due to dilution of the conducting component. Samples coated with PEDOT:PSS blends containing N‐methylpyrrolidone (NMP) or dimethyl sulfoxide (DMSO) exhibited a higher conductivity than those coated with pure PEDOT:PSS because of their plasticizing effect and conformational changes of PEDOT molecules indicated by the red shift and disappearance of the shoulder peak at about 1442 cm^?1 in the Raman spectra of the coated samples. EDS imaging showed that PEDOT:PSS is distributed throughout the thickness direction of the paper. Contact angle measurements were made to monitor the hydrophilicity of the paper surface and total sulfur analysis was used to determine the amount of PEDOT:PSS deposited onto the paper. The tensile strength of all the paper samples increased slightly after treatment. Thus, it is demonstrated that enhanced bulk conductivity in the order of 10^?3 S/cm can be achieved by using organic conductive materials and surface treatment techniques. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Enhanced thermoelectric performance by alcoholic solvents effects in highly conductive benzenesulfonate‐doped poly(3,4‐ethylenedioxythiophene)/graphene composites

Benzenesulfonate‐doped poly(3,4‐ethylenedioxythiophene) (PEDOT‐Bzs)/graphene thermoelectric (TE) composites with various graphene filler contents were synthesized in five different kinds of solvents. Dodecylbenzenesulfonic acid (DBSA) was used to achieve good dispersion of graphene into the PEDOT matrix. Among the synthesized PEDOT materials, the one synthesized in methanol (PEDOT‐MeOH) had the highest electrical conductivity. X‐ray photoelectron spectroscopy (XPS) analysis showed almost the same charge carrier concentration for all PEDOT materials. However, the X‐ray diffraction (XRD) analysis highlighted the enhancement of PEDOT chain stacking by shorter‐chain alcoholic solvents, as a result of which the carrier mobility and electrical conductivity were increased. The electrical conductivity and the Seebeck coefficient of the PEDOT/graphene composites were significantly improved with increasing the graphene content, which strongly depended on increased carrier mobility. The thermal conductivity of the composites exhibited relatively small changes, attributed to phonon scattering effects. The maximum TE efficiency of the PEDOT‐MeOH/graphene composite with 75 wt % graphene showed a substantially improved value of 1.9 × 10^?2, higher than that of the other PEDOT/graphene composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42107.     

Enhanced thermoelectric performance of poly(3,4‐ethylenedioxythiophene):poly(4‐styrenesulfonate) (PEDOT:PSS) with long‐term humidity stability via sequential treatment with trifluoroacetic acid

This paper reports a range of effective sequential chemical processes to enhance the thermoelectric performance of conducting poly(3,4‐ethylenedioxythiophene) films doped with poly(styrene sulfonate) anions (PEDOT:PSS). The electrical conductivity of the PEDOT:PSS films was significantly increased from 0.33 to 3748 S cm^?1 after a series of sequential treatments with trifluoroacetic acid (TFA) while the Seebeck coefficient and thermal conductivity were slightly reduced from 17.5 ± 1.2 to 16.0 ± 1.1 μV K^?1 and 0.537 to 0.415 W m^–1 K^?1 for the pristine film and treated film, respectively, leading to a significant improvement in power factor up to 97.1 ± 5.4 μW m^–1 K^?2. More importantly, around 80% of the electrical conductivity and Seebeck coefficient was retained after 20 days for these TFA‐treated PEDOT:PSS films, revealing the potential for real thermoelectric applications. © 2019 Society of Chemical Industry     

Behavior of polyoxyethylene‐containing interpenetrating polymer networks and their LiCLO4 complexes as phase transfer catalysts and ionic conductors

Simultaneous grafted interpenetrating polymer networks (IPNs) based on [castor oil–poly(ethylene glycol) (PEG)] polyurethane and poly(alkyl methacrylate) were synthesized by simultaneously coupling castor oil and PEG with 2,4‐toluene diisocyanate and by radical polymerization of alkyl methacrylate with castor oil. The gel content of the IPNs is ～96% in most cases. The IPNs were characterized by infrared spectroscopy. The effects of compositional variation of the IPNs on phase transfer catalytic efficiency and mechanical properties, and conductivity of the IPNs complexed with LiClO₄ were also studied. The results show that the IPNs have good phase transfer catalytic ability in the Williamson reaction and exhibit a maximum conversion of potassium phenolate at 55% polyoxyethylene (PEO). The phase transfer catalytic ability of the IPN increases with molecular weight of PEG used in the IPN synthesis and with the length of alkyl groups of the grafts, but decreases with increasing crosslinking degree. The complex of the IPNs with LiClO₄ exhibits good ionic conductivity at room temperature in the range 10^?5–3 × 10^?4 S/cm. This ionic conductivity decreases with increasing either the crosslinking degree or the molecular weight of PEG used, but increases with increasing PEO content. The more compatible are the grafts with PEO, the lower is the conductivity. Either butyl methacrylate or ethyl methacrylate is a good choice for the monomer in the synthesis of the IPNs for use as phase transfer catalysts and ion conducting materials. The IPNs showed high tensile strength in the range 10–20 MPa. The good mechanical properties of the IPNs favor their applications as a strong solid polymer electrolyte film and an easily recoverable phase transfer catalyst. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 830–836, 2003     

Chemical cross-linking of conducting poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) using poly(ethylene oxide) (PEO)

Hybrid films of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) were prepared with different molecular weights of poly(ethylene oxide) (PEO). The cross-linking reaction between PEO and PEDOT:PSS was performed at high temperature and confirmed by using differential scanning calorimeter (DSC), contact angle measurement, and solid-state ¹H NMR. The effect of chemical reaction on the conductivity and morphology of these hybrid films was studied by using 4-point probe and atomic force microscope (AFM), respectively. As-spun PEO/PEDOT:PSS films have lower electric conductivity due to the addition of nonconductive PEO, and exhibits no molecular weight dependence on conductivity. After chemical cross-linking reaction at high temperature, only PEDOT:PSS films with lowest molecular weight PEO additives show enhanced conductivity with increasing reaction time. AFM result indicates that the heat-treated PEO/PEDOT:PSS hybrid films show grain-like morphology compared to ethylene glycol treated PEDOT:PSS films which shows continuous PEDOT domain. In the present work we demonstrate that the cross-linking reaction can be used to improve the wet stability of PEDOT:PSS nanofiber, showing good water resistance and excellent dimensional stability.     

Shape memory properties and unusual optical behaviour of an interpenetrating network of poly(ethylene oxide) and poly(2‐hydroxyethyl methacrylate)

An interpenetrating polymer network (IPN) with shape memory properties was prepared by using poly(2‐hydroxyethyl methacrylate) (PHEMA) and poly(ethylene oxide) (PEO). PHEMA acts as a fixed phase and PEO as a switching phase. The switching action of PEO is due to the reversible process of melting and crystallization. It was observed that the shape recovery of the IPN increases with increasing crosslinker concentration up to an optimum value and decreases thereafter. In addition to the shape memory property, the IPNs show a reversible change in optical properties from translucent to opaque. The change in optical properties is quite different from that observed in a semicrystalline polymer system where the transparency increases as a result of the melting of crystals. This behaviour of the IPN is explained in terms of H‐bonding of PEO with PHEMA. Fourier transform infrared spectroscopy was used to study the H‐bonding between PEO and PHEMA. © 2019 Society of Chemical Industry     

Sulfonated polyimide and poly (ethylene glycol) diacrylate based semi‐interpenetrating polymer network membranes for fuel cells

Semi‐interpenetrating polymer network (semi‐IPN) membranes based on novel sulfonated polyimide (SPI) and poly (ethylene glycol) diacrylate (PEGDA) have been prepared for the fuel cell applications. SPI was synthesized from 1,4,5,8‐naphthalenetetracarboxylic dianhydride, 4,4′‐diaminobiphenyl 2,2′‐disulfonic acid, and 2‐bis [4‐(4‐aminophenoxy) phenyl] hexafluoropropane. PEGDA was polymerized in the presence of SPI to synthesize semi‐IPN membranes of different ionic contents. These membranes were characterized by determining, ion exchange capacity, water uptake, water stability, proton conductivity, and thermal stability. The proton conductivity of the membranes increased with increasing PEGDA content in the order of 10^?1 S cm^?1 at 90°C. These interpenetrating network membranes showed higher water stability than the pure acid polyimide membrane. This study shows that semi‐IPN SPI membranes based on PEGDA which gives hydrophilic group and structural stability can be available candidates comparable to Nafion® 117 over 70°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and characterization of thermosensitive poly(N‐isopropylacrylamide)/poly(ethylene oxide) semi‐interpenetrating polymer networks

Temperature‐sensitive poly(N‐isopropylacrylamide) hydrogels were successfully synthesized by using poly(ethylene oxide) as the interpenetrating agent. The newly prepared semi‐interpenetrating polymer network (semi‐IPN) hydrogels exhibited much better properties as temperature‐sensitive polymers than they did in the past. Characterizations of the IPN hydrogels were investigated using a swelling experiment, FTIR spectroscopy, and differential scanning calorimetry (DSC). Semi‐IPN hydrogels exhibited a relatively high temperature dependent swelling ratio in the range of 23–28 at room temperature. DSC was used for the determination of the lower critical solution temperature of the semi‐IPN hydrogel. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3032–3036, 2003     

Preparation and properties of alkaline anion exchange membrane with semi‐interpenetrating polymer networks based on poly(vinylidene fluoride‐co‐hexafluoropropylene)

Alkaline anion exchange membrane with semi‐interpenetrating polymer network (s‐IPN) was constituted based upon quaternized poly(butyl acrylate‐co‐vinylbenzyl chloride) (QPBV) and poly(vinylidene fluoride‐co‐hexafluoropropylene) [P(VDF‐HFP)]. The QPBV was synthesized via the free radical copolymerization, followed by quaternization with N‐methylimidazole. The s‐IPN system was constituted by melting blend of QPBV and P(VDF‐HFP), and then crosslinking of P(VDF‐HFP). Ion exchange capacity, water uptake, mechanical performance, and thermal stability of these membranes were characterized. TEM showed that alkaline anion exchange membrane exhibited s‐IPN morphology with microphase separation. The fabricated s‐IPN membrane exhibited hydroxide ion conductivity up to 15 mS cm^?1 at 25 °C and a maximum DMFC power density of 46.55 mW cm^?2 at a load current density of 98 mA cm^?2 at 30 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45775.     

Electrical conductivity of polymer blends of poly(3,4-ethylenedioxythiophene): Poly(styrenesulfonate): N-methyl-2-pyrrolidinone and polyvinyl alcohol

The goal of this study is to determine the electrically conductivity of the polymers poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate): N-methyl-2-pyrrolidinone (PEDOT: PSS: NMP) and PEDOT: PSS when blended with polyvinyl alcohol (PVA). While the conducting polymers have high conductivity when not blended with PVA, they are brittle and difficult to spin-coat. Thus, the motivation for this study is to develop blends of these two conducting polymers with PVA to produce a material with optimized mechanical properties and that can also be spin-coated. The blends are produced using aqueous preparations of these materials. Mixtures of various weight percentages (wt %) of PEDOT: PSS: NMP and PEDOT: PSS are prepared and spin-coated on glass slides to form thin films. In the blends, the film conductivity increases with increasing content of either PEDOT: PSS: NMP or PEDOT: PSS. For example, 100 wt % of PEDOT: PSS: NMP and 60 wt % of PEDOT: PSS: NMP blended with PVA exhibit conductivities of, respectively, 10 and 4.02 S/cm. In contrast, conductivities of only 0.0525 and 0.000506 S/cm are observed, respectively, for 100 wt % of PEDOT: PSS and 60 wt % of PEDOT: PSS content in the PEDOT: PSS/PVA blends (No NMP). The addition of the NMP enhances the electrical conductivity by two to five orders of magnitude (depending on the amount of PVA in the blend) due to conformational change of PEDOT chains. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The influence of thermal cycling and compressive force on the resistance of poly(3,4‐ethylenedioxythiophene)/poly(4‐styrenesulfonic acid)‐coated surfaces

There is an increasing interest in the use of conducting polymers for a wide variety of applications. This includes the study and development of alternative contact‐connector materials. The main aim is to achieve overall improvements in performance as well as cost effectiveness. Currently, extrinsic conducting polymers (ECPs) are employed as conductive coats or adhesives at contact interfaces. However, frictional abrasion within the metal‐doped polymer (ECP) causes instability in the resistance. It is important to overcome this fretting effect, especially in automotive applications; hence, the possibilities of employing intrinsically conducting polymers (ICPs) are explored. Flat contact film coatings have been fabricated in‐house using poly(3,4‐ethylenedioxythiopene)/poly(4‐styrenesulfonic acid) (PEDOT/PSS) with dimethylformamide as the secondary solvent. Resistance is measured using the four‐wire method. The conductivities of the PEDOT/PSS‐coated contacts are found to be in the order of 10^?2 S cm^?1. The change of resistance under varying compression forces has been found to be repeatable. The thermal effects on these contacts are also studied and the results are depicted as exponential negative temperature coefficients of resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2445–2452, 2006     

Interpenetrating polymer networks of poly(butyl methacrylate) and poly(α‐terpineol‐co‐styrene): Synthesis and characterization

Simultaneous interpenetrating polymer networks (IPNs) based on poly(butyl methacrylate) and poly(α‐terpineol‐co‐styrene) were synthesized with azobisisobutyronitrile (AIBN) as the initiator and divinyl benzene as the crosslinking agent in xylene under an inert nitrogen atmosphere. Fourier transform infrared spectra provided structural evidence for the IPNs, indicating characteristic frequencies of ester groups of butyl methacrylate at 1723 cm^?1 and alcoholic groups of α‐terpineol at 3436 cm^?1. Scanning electron microscopy revealed threadlike network structures. Properties such as percentage swelling and average molecular weight between crosslinks were direct functions of the copolymer and initiator (AIBN) concentrations and inverse functions of the monomer (butyl methacrylate) and crosslinking agent (divinyl benzene) concentrations. Differential scanning calorimetry showed an IPN glass‐transition temperature at 80.2°C. The thermal decompositions of the IPNs were established with the help of thermogravimetric analysis. The value of the activation energy, calculated from thermogravimetric analysis with the Coats and Redfern equation, was 23 kJ/mol. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 343–352, 2006     

Effects of alcoholic solvents on the conductivity of tosylate‐doped poly(3,4‐ethylenedioxythiophene) (PEDOT‐OTs)

The effects of alcoholic solvents on the charge transport properties of tosylate‐doped poly(3,4‐ethylenedioxythiophene) (PEDOT‐OTs) are investigated. The use of different alcoholic solvents in the oxidative chemical polymerization of 3,4‐ethylenedioxythiophene (EDOT) with iron(III)‐p‐tosylate led to a change in the electrical conductivity of PEDOT‐OTs. For example, PEDOT‐OTs prepared from methanol shows a conductivity of 20.1 S cm^?1 which is enhanced by a factor of 200 as compared to PEDOT‐OTs prepared from hexanol. The variation of charge transport properties on the use of different alcoholic solvents is consistent with the data recorded by UV‐visible and electrospin resonance (ESR) measurements. From XPS experiments, the PEDOT‐OTs samples prepared from different alcoholic solvents were found to have almost the same doping level, suggesting that the number of charge carriers is not responsible for the change in conductivity. Supported by XRD results, it was found that the use of alcoholic solvents with shorter chain length induces more efficient packing of PEDOT chains. It is proposed that the alcoholic solvents associated with the counter ion of PEDOT via hydrogen bonding give rise to a change in the molecular ordering of PEDOT chains during the polymerization step, hence enhancing or depressing the inter‐chain hopping rate of the resulting PEDOT‐OTs. Copyright © 2005 Society of Chemical Industry     

Preparation and performance of a transparent poly(3,4‐ethylene dioxythiophene)–poly(p‐styrene sulfonate‐co‐acrylic acid sodium) film with a high stability and water resistance

Poly(p‐styrene sulfonate‐co‐acrylic acid sodium) (PSA) from the copolymerization of acrylic acid sodium and p‐styrene sulfonate monomers were used to dope poly(3,4‐ethylene dioxythiophene) (PEDOT) to generate PEDOT–PSA antistatic dispersions. Compared to those of the PEDOT–poly(p‐styrene sulfonate sodium) (PSS), the physical and electrical properties of the PEDOT–PSA conductive liquids were much better. The PEDOT–PSA films possessed a better water resistance without a decrease in the conductivity. The sheet resistance of the PEDOT–PSA–poly(ethylene terephthalate) (PET) films was about 1.5 × 10⁴ Ω/sq with a 100 nm thickness, the same as the PEDOT–PSS–PET films. The transmittance of the PEDOT–PSA–PET films exceeded 88%. Furthermore, the environmental dispersity of the PEDOT–PSA antistatic dispersion was apparently improved by the dopant PSA so that the stability was extraordinarily promoted. Meanwhile, the water resistances of the PEDOT–PSA–PET and PEDOT–PSA films were also enhanced. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45163.     

Proton‐conducting gel polyelectrolytes based on Lewis acid

A novel proton‐gel‐conducting polymer electrolyte was prepared by blending boron trifluoride diethyl etherate with poly(ethylene oxide) (PEO), glycerol, and propylene carbonate (PC) at certain molar ratios. The electrolytes exhibited ambient conductivity from 10^?5 to 10^?3 S/cm. DSC results indicated that the electrolytes were amorphous. The ¹H‐NMR and Raman spectra showed strong interactions between the Lewis acid and the hydroxyl groups both of glycerol and of PEO. This resulted in the formation of protons for ionic conduction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1267–1272, 2003     

Electrochemical behavior of an interpenetrating polymer network hydrogel composed of poly(propylene glycol) and poly(acrylic acid)

An interpenetrating polymer network (IPN) hydrogel based on poly(propylene glycol) and poly(acrylic acid) was prepared by UV irradiation. The swelling behavior of the IPN hydrogel was studied by the immersion of the gel in aqueous NaCl solutions of various concentrations. The swelling ratio decreased with an increase in the NaCl concentration. The electrically sensitive behavior of the IPN hydrogel in electric fields was also investigated. The IPN hydrogel also showed a stepwise bending behavior that depended on the electric stimulus. The bending angle and bending speed of the IPN hydrogel were greatest in 0.6 wt % aqueous NaCl and increased with an increase in the applied voltage. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2301–2305, 2003     

Design and electrical conductivity of poly(acrylic acid‐g‐gelatin)/graphite conducting gel

A novel poly(acrylic acid‐g‐gelatin)/graphite composite is synthesized by aqueous solution polymerization. Based on the electrical conductivity of graphite nanoplatelets and the absorbency of poly(acrylic acid‐g‐gelatin)/graphite, a novel conducting gel with a conductivity of 3.18 mS cm^?1 is prepared. The effects of synthesis parameters on the electrical conductivity of the gels are investigated in detail. An appended network structure model of the poly(acrylic acid‐g‐gelatin)/graphite conducting gel is proposed. The conducting gel presents a high mechanical strength in cyclohexane, which is important for the gel applications. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Water sorption of poly(vinyl alcohol)/ poly(diallyldimethylammonium chloride) interpenetrating polymer network hydrogels

Temperature‐responsive interpenetrating polymer network (IPN) hydrogels constructed with poly(vinyl alcohol) and poly(diallyldimethylammonium chloride) using the sequential IPN method were studied. The characteristics of IPN hydrogels were investigated using the dynamic vapor sorption system. IPN hydrogels exhibited a relatively high sorption ratio, 180–360% at room temperature. The sorption ratio of hydrogels depended on temperature. Diffusion coefficients were calculated according to the Fickian Law at several temperatures. The apparent activation energy was 5.43 kJ mol^?1, which corresponds to typical diffusion processes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1389–1392, 2003