New ionic polymer–metal composite actuators based on PVDF/PSSA/PVP polymer blend membrane

Ionic polymer–metal composite (IPMC) actuators that display continuously large actuation displacements without back relaxation and with large blocking force at low direct current (DC) voltages are used as biomimetic sensors, actuators and biomedical devices. This article reports the preparation and actuation performance of new IPMC actuators based on the polyvinylidene fluoride (PVDF)/polystyrene sulfonic acid (PSSA)/polyvinyl pyrrolidone (PVP) polymer blend membrane, which requires low voltage DC. The performance results of the proposed IPMC actuators are compared with Nafion‐based IPMC actuators. In the blend membrane, PVDF is the hydrophobic polymer, PSSA is the polyelectrolyte, and PVP is the hydrophilic basic polymer. The proposed IPMC actuators based on the PVDF/PSSA/PVP blend membrane of polymer mixture ratios of 60/15/25 and 50/25/25 gave higher actuation displacement and higher blocking force at low DC voltages than the Nafion‐based IPMC actuator. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Preparation and self‐assembly of polyaniline nanorods and their application as electroactive actuators

To improve the performance of ion‐exchange polymer–metal composite (IPMC) actuators, an electrical pathway material for enhancing the surface adhesion between the membrane and the metal electrodes of the IPMC was studied. As an efficient electrical pathway material, polyaniline nanorods (PANI‐NRs) doped with p‐toluene sulfonic acid (TSA) were synthesized with a template‐free method. The factors affecting polyaniline morphology were studied with various dopant concentrations and oxidant feeding rates. Highly conductive PANI‐NRs were formed when they were synthesized with ammonium persulfate at a 5.0 mL/min oxidant feeding rate and doped with 0.125M TSA. The conductivity of the PANI‐NRs was 1.15 × 10^?1 S/cm, and their diameters and lengths were 120–180 nm and 0.6–2 μm, respectively. To apply the membrane as an actuator, perfluorosulfonated ionomer (Nafion)/PANI‐NR blends were prepared by solution blending and casting. The actuating ability of the three‐layered membrane consisting of Nafion/PANI‐NR blends was then examined and compared with that of Nafion only. The actuating ability of the IPMC was improved when Nafion/PANI‐NRs were used as electrical pathways. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The influence of solvent properties on the performance of polysulfone/β‐cyclodextrin polyurethane mixed‐matrix membranes

This study investigates the effect of solvent properties on the structural morphology and permeation properties of polysulfone/β‐cyclodextrin polyurethane (PSf/β‐CDPU) mixed‐matrix membranes (MMMs). The membranes were prepared by a modified phase‐inversion route using four different casting solvents [dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), dimethyl acetamide (DMA), and N‐methyl‐2‐pyrrolidone (NMP)]. While DMSO‐based membranes demonstrated particularly high permeability (ca 147 L/m²h.bar), their crystallinity was low compared to MMMs prepared using DMA, DMF and NMP due to the formation of thin active layers on their surfaces. Cross‐sectional morphology revealed that the MMMs have a dense top skin with finger‐like inner pore structures. Membranes prepared using NMP displayed the highest hydrophilicity, porosity, and crystallinity due to the low volatility of NMP; DMF membranes exhibited superior mechanical and thermal stability due to its (DMF) high hydrogen bonding (δH) values. Thus, the morphological parameters, bulk porosity, and flux performance of MMMs have a significant inter‐relationship with the solubility properties of each solvent (i.e., δH, density, volatility, solubility parameter). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2005–2014, 2013     

Easy,operable ionic polymer metal composite actuator based on a platinum‐coated sulfonated poly(vinyl alcohol)–polyaniline composite membrane

In this study, an electric‐stimulus‐responsive bending actuator based on a platinum (Pt)‐coated sulfonated poly(vinyl alcohol) (SPVA)–polyaniline (PANI) composite membrane was developed. The SPVA–PANI membrane was prepared by a solution casting method; it showed good electrochemical properties and an adequate ion‐exchange capacity of 1.6 mequiv/g of dry membrane. The water uptake by the membrane with 4 h of immersion time at 45 °C was found to be 425%. The SPVA–PANI composite membrane based ionic polymer metal composite (IPMC) actuator prepared by the coating of Pt metal layers on both sides of the membrane by an electroless plating process showed a good proton conductivity of 1.75 × 10^?3 S/cm. The smooth and uniform coating of Pt on both surfaces of the membrane, as indicated by scanning electron micrographs, seemed to be responsible for the slow water loss that is necessary for the long life of an IPMC actuator. The maximum water loss was 48% at 6 V for 12 min. This indicated the better performance of the IPMC membrane when an electric potential was applied. According to electromechanical characterization, the maximum tip displacement was 14.5 mm at 5.25 V. A multifinger IPMC membrane based microgripping system was developed, and it showed potential for microrobotics application. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43787.     

Preparation and characterization of polysulfone–cyclodextrin composite nanofiltration membrane: Solvent effect

α-Cyclodextrin membranes were prepared by the phase inversion method using four types of casting solvents such as N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethyl acetamide (DMAc), and dimethyl formamide (DMF) herein-after termed as α-CD-NMP, α-CD-DMSO, α-CD-DMAc, and α-CD-DMF, respectively. The membranes were characterized by IR, XRD, TGA-DTA, DSC, and SEM analysis and show that solvents like NMP, DMA, DMF give good uniform morphological membranes and are better than that of DMSO. Thermal decompositions of the pure polymer and composite membranes indicate different range of thermal degradation of the membrane. This study reveals that the casting solvents NMP, DMF, DMAC have nearly same significant effect on morphology and other properties of the membranes. This is explained in terms of demixing behavior of the polymer and the combined effect of solvent volatility and polymer–solvent interactions as estimated from Hansen solubility parameter. Solvent hydrophobicity also affects the performance of the membrane and can be determined in terms of water permeability. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fabrication and applied investigation of a muscle‐like linear actuator using lonic polymer metal composites

Focusing on the existing issues of ionic polymer metal composites (IPMC), for example, little force output and swing motion, and the applied requirements in the biomimetic artificial muscles using as the actuators, under the current framework, a muscle‐like linear actuator based on the combination of Bi‐IPMC linear actuator unit, whose experimental characteristics have been discussed in our previous work, was fabricated. The performance investigation showed that it can generate a linear movement type like artificial muscle, and there is an prominent improvement of force output capabilities compared with Bi‐IPMC linear actuator unit. Also, based on the 3D printing technique, a bionic jumping robot was experimented using the fabricating muscle‐like linear actuator, and the experimental result was validated against the feasibility of muscle‐like linear actuator. POLYM. COMPOS., 38:147–156, 2017. © 2015 Society of Plastics Engineers     

Synthesis and characterization of homogeneously sulfonated poly(ether ether ketone) membranes: Effect of casting solvent

Poly(ether ether ketone) (PEEK) was homogeneously sulfonated to have various degrees of sulfonation from 48 to 83%. The sulfonated PEEK (sPEEK) membranes were prepared by a solvent casting method using a few solvents such as N,N‐dimethyl formamide, N,N‐dimethyl acetamide, and 1‐methyl‐2‐pyrrolidinone. The effect of casting solvent on the membrane morphology and properties was investigated. The sulfonation degree and ion exchange capacity were determined by a back titration method, and the morphology of membrane by SEM. It has been demonstrated that the surface morphology and properties of sPEEK membranes, such as water uptake, methanol permeability, ion conductivity, and mechanical strength, were considerably affected by the type of solvent, where the DMAC‐sPEEK system showed the best performance in the polymer electrolyte membrane application for DMFC. This solvent effect on the membrane morphology and properties was caused by interaction strength (hydrogen bonding) between polymer and solvent. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The Enhancement Effect of Mesoporous Graphene on Actuation of Nafion‐Based IPMC

A facile method to fabricate ionic polymer‐metal composite (IPMC) actuators is proposed. A blend of mesoporous graphene (MG) and Nafion is used as the ionic matrix, which is sandwiched by two layers of blend of reduced graphene oxide (rGO) and Nafion as the electrodes. When subjected to an electrical field of 3 V, the IPMC actuator exhibits a blocking force of 10 gf g^?1 for 20 s, and the same behavior can be repeatedly played for hundreds of cycles. MG improves the mechanical properties of Nafion‐based IPMC, more importantly, the mesopores in graphene provide additional pathway for the diffusion of cationic clusters and thus enhance the actuation speed. In addition, the surface electrodes of rGO protect the interlamellar liquid from evaporation thus ensure the durability.

     

Modification of Nafion membrane using poly(4‐vinyl pyridine) for direct methanol fuel cell

Perfluorinated membrane such as Nafion (from Du‐Pont) has been used as a polymer electrolyte membrane. Nafion 117 membrane, which was usually used as the electrolyte membrane for the polymer electrolyte membrane fuel cell (PEMFC), was modified by using poly(4‐vinyl pyridine) (P4VP) to reduce the methanol crossover, which cause fuel losses and lower power efficiency, by the formation of an ionic crosslink structure (sulfonic acid‐pyridine complex) on the Nafion 117 surface. Nafion film was immersed in P4VP/N‐methyl pyrrolidone (NMP) solution. P4VP weight percent of modified membrane was controlled by changing the concentration of P4VP/NMP solution and the dipping time. P4VP weight percent increased with increasing concentration of dipping solution and dipping time. The thickness of the P4VP layer increased with increasing concentration of dipping solution and dipping time when the concentration of the dipping solution was low. At high P4VP concentration, the thickness of the P4VP layer was almost constant owing to the formation of acid–base complex which interrupted the penetration of P4VP. FTIR results showed that P4VP could penetrate up to 30 µm of Nafion 117 membrane. Proton conductivity and methanol permeability of modified membrane were lower than those of Nafion 117. Both decreased with increasing concentration of dipping solution and dipping time. Methanol permeability was observed to be more dependent on the penetration depth of P4VP. Water uptake of the modified membrane, the important factor in a fuel cell, was lower than that of Nafion 117. Water uptake also decreased with increasing of P4VP weight. On the basis of this study, the thinner the P4VP layer on the Nafion 117 membrane, the higher was the proton conductivity. Methanol permeability decreased exponentially as a function of P4VP weight percent. Copyright © 2006 Society of Chemical Industry     

Effect of various additives on pore size of polysulfone membrane by phase‐inversion process

The phase‐inversion process was used to prepare integrally skinned asymmetric polysulfone (PSf) membranes with different pore sizes. Membranes were prepared from a casting solution of PSf; N‐methyl‐2‐pyrrolidone (NMP) as solvent; and 1,4‐dioxane, diethylene glycol dimethyl ether (DGDE), acetone, and γ‐butyrolactone (GBL) as additives by immersing them in water as a coagulant. The effect of the additives on membrane performance and structure was investigated. The low miscibility of 1,4‐dioxane, DGDE, and acetone with the coagulant resulted in reduced membrane pore size. However, by using GBL as additive pore size of the membrane was slightly increased because of its higher miscibility with the coagulant than NMP. Changing the amount of additives in the casting solution could control the molecular‐weight cutoff values of asymmetric membranes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2562–2566, 2003     

Polymer complex from copolymers of acrylonitrile and ionic vinyl benzyl compounds

Copolymerization of sodium vinyl benzyl sulfonate (VBS) or vinyl benzyl trimethyl ammonium chloride (VBQ) with acrylonitrile (AN) gave polyelectrolytes of preferable solution viscosities. The blending of these two copolymers in N,N-dimethyl formamide (DMF) produced polymer complexes with ionic linkages, of which the following properties were examined. The maximum in the tan δ temperature was increased by complex formation. Freundlich-type dye adsorption and much better dyeability than on polyacrylonitrile was observed. Electric resistivity decreased with the introduction of ionic moiety. Permeability of water increased with the number of ionic sites. Homogeneous films could be cast from DMF and dimethyl sulfoxide (DMSO) solutions.     

Solubility parameter-based analysis of polyacrylonitrile solutions in N,N-dimethyl formamide and dimethyl sulfoxide

The physical properties of the solutions of polyacrylonitrile (PAN) in N,N-dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) were characterized in terms of solubility parameter. The physical properties were largely determined by individual solubility parameters, particularly the polar term, rather than overall solubility parameter. With increasing temperature, the intrinsic viscosity and hydrodynamic diameter of dilute solutions were decreased but the dynamic viscosity (η′) of concentrated solutions was increased. Of the two solvents, these phenomena were more pronounced with DMF; DMF gave greater η′ and yield stress than DMSO. When the polymer solutions were dried at 25 °C DMSO generated a cocontinuous structure whereas DMF produced a dispersed morphology. In addition, DMF dissolved PAN faster than DMSO, and the dissolution process followed a mechanism analogous to S_N2 reaction.     

Preparation and gel properties of poly(ether ether ketone) with pendent sulfonimide groups

Poly(ether ether ketone) with pendent sulfonimide groups (B‐SPEEK) was prepared from poly(ether ether ketone), sulfuric acid, thionyl chloride, para‐toluene sulfonate, and pyridine. The prepared B‐SPEEK was characterized by Fourier transform infrared spectroscopy, ¹H‐NMR, and thermogravimetric analysis. The swelling of the gels was examined in N,N‐dimethylacetamide (DMAC), N,N‐dimethylformamide (DMF), 1‐methyl‐2‐pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), and a DMSO/water mixture. The gel showed extremely high swelling in DMSO, DMF, DMAC, and NMP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1058‐1063, 2013     

Chemical modification and dechlorination of polyvinyl chloride by substitution with thiocyanate as a nucleophile

This study examined the chemical modification of polyvinyl chloride (PVC) by substitution with SCN (thiocyanate) as a nucleophile. The effects of temperature, molar SCN/Cl ratio, and solvent on the substitution by SCN and the elimination of HCl were investigated. In SCN/EG (ethylene glycol) solution, the substitution/dechlorination ratio increased with decreasing temperature. The dechlorination yield increased with an increasing molar SCN/Cl ratio, favoring the substitution over the elimination. When N,N‐dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) solutions were used as solvents, DMF favored the substitution, whereas DMSO favored the elimination. In the SCN/DMF solution, the substitution yield and the substitution/dechlorination ratio increased with increasing temperature. Higher temperatures favored the substitution over the elimination in SCN/DMF. Furthermore, the reaction of PVC in SCN/tetrahydrofuran (THF)‐DMSO (1:2) proceeded at room temperature, favoring the substitution over elimination. The isomerization of SCN was observed, resulting only in ? N?C?S (isothiocyanate) at room temperature and ? S? C?N (thiocyanate) at 190°C. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Effect of mixed solvents on phase inversion of polymeric membranes

The thermodynamics of phase inversion of polyvinylidene fluoride membrane with mixed solvents (N,N‐dimethyl formamide (DMF) and acetone) were modeled using Flory–Huggins theory. The kinetics of phase inversion were studied by measuring solvent concentration in the precipitation bath. A model was proposed to predict the time‐dependent solvent concentration profile in the precipitation bath. Depending on solvent volatility, the duration of the kinetics‐dominated regime and the evaporation‐dominated regime varies. A comparative analysis of thermodynamic and kinetic factors was used to predict membrane morphology and it was observed that the system under consideration was thermodynamics dominated. The membrane porosity exhibited decreasing porosity up to the Ac60 membrane (acetone to DMF ratio 60) and thereafter the membrane sublayer showed small pores. Addition of acetone resulted in increased crystallinity and surface hydrophilicity. The mean flow pore diameter measured using a liquid–liquid porometer decreased from 105 nm for an Ac0 membrane (acetone to DMF ratio 0) to 17 nm for an Ac60 membrane. Correspondingly, the molecular weight cut‐off of the membranes decreased from 135 kDa (for the Ac0 membrane) to 104 kDa (for the Ac60 membrane). The model proposed in this work can be used as a tool to predict the properties of intermediate compositions and prepare tailor‐made membranes with desired properties. © 2020 Society of Chemical Industry     

Potential of DMSO as greener solvent for PES ultra‐ and nanofiltration membrane preparation

In this article, the performance of polyethersulfone (PES) ultra‐ and nanofiltration membranes, prepared with the non‐toxic solvent dimethyl sulfoxide (DMSO), was investigated. The membranes were prepared by immersion precipitation via phase inversion. Experimental results proved that DMSO is a better alternative to N‐methyl‐2‐pyrrolidone (NMP) as solvent for PES ultrafiltration membranes as the membranes had a higher permeability and rejection of bovine serum albumin (BSA). An explanation was found based on experimental cloud point data and scanning electron microscopy images showing the morphology. The rejection of BSA and rose Bengal (RB) was proportional to the polymer concentration. On the contrary, the permeability decreased with increasing polymer concentration. For a casting thickness of 250 µm, an optimal balance between permeability and rejection of macromolecules for ultrafiltration was found at 24 wt % PES. The permeability was inversely proportional to the casting thickness, but a small decrease in rejection was observed when lowering the thickness. A good balance between permeability and rejection of RB was found, using a reference nanofiltration membrane of 28.5 wt % PES with 150 µm casting thickness. This membrane achieved a RB rejection of 95.3% and a pure water flux of 2.03 L m^?2 h^?1 bar^?1. The membrane thickness and polymer concentration did not have a clear influence on the hydrophilicity of the membranes. It can be concluded that DMSO is a benign alternative as compared to traditional solvents such as NMP and also results in better PES membrane performances. DMSO is a perfectly suitable solvent for ultrafiltration applications and has potential to be used for nanofiltration applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46494.     

Thorium (IV) phosphate‐polyaniline composite‐based hydrophilic membranes for bending actuator application

In the present study, ionic polymer metal composite (IPMC) membrane actuator based on triple‐layered thorium(IV) phosphate/polyaniline/Pt (ThP‐PANI‐Pt) was prepared via consecutive solution recasting and electroless plating methods. The triple‐layered membrane is composed of thorium(IV) phosphate (ThP) inorganic cation exchanger layer in the middle section, two layers of polyaniline deposited through in situ polymerization and finally Pt electrode layers on both the surfaces on the outer section. The water uptake capacity of the ThP‐PANI composite polymer membrane was found to be 95.40% at 45ºC for 10 h of immersion time. The ion exchange capacity and proton conductivity was found to be 1.6 meq g^?1of dry membrane and 1.12 × 10^?3 S cm^?1, respectively. Maximum water loss from IPMC was 38% at 4 V for a time period of 12 min. Scanning electron micrographs shows the smooth and uniform coating of Pt on both side of composite polymer membrane surfaces. Cyclic voltammetry, linear sweep voltammetry, transmission electron microscopy, Fourier transforms infrared spectroscopy, thermal gravimetric analysis, X‐ray diffraction, and tip displacement of ThP‐PANI‐Pt IPMC membrane actuator was also examined. POLYM. ENG. SCI., 57:258–267, 2017. © 2016 Society of Plastics Engineers     

Synthesis and structural characterization of novel chiral nanostructured poly(esterimide)s containing different natural amino acids and 4,4′‐thiobis(2‐tert‐butyl‐5‐methylphenol) linkages

Pyromellitic dianhydride (benzene‐1,2,4,5‐tetracarboxylic dianhydride) (1) was reacted with several amino acids in acetic acid and the resulting imide‐acid [N,N′‐(pyromellitoyl)‐bis‐L ‐amino acid diacid] (4a–4d) was obtained in high yield. The direct polycondensation reaction of these diacids with 4,4′‐thiobis(2‐tert‐butyl‐5‐methylphenol) (5) was carried out in a system of tosyl chloride(TsCl), pyridine, and N,N‐dimethyl formamide (DMF) to give a series of novel optically active poly(esterimide)s. Step‐growth polymerization was carried out by varying the time of heating and the molar ratio of TsCl/diacid, and the optimum conditions were achieved. These new chiral polymers were characterized with respect to chemical structure and purity by means of specific rotation experiments, FTIR, ¹H‐NMR, X‐ray diffraction, elemental, and thermogravimetric analysis (TGA) field emission scanning electron microscopy (FE‐SEM) techniques. These polymers are readily soluble in many polar organic solvents like DMF, N,N‐dimethyl acetamide, dimethyl sulfoxide, N‐methyl‐2‐pyrrolidone, and protic solvents such as sulfuric acid. TGA showed that the 10% weight loss temperature in a nitrogen atmosphere was more than 390°C; therefore, these new chiral polymers have useful levels of thermal stability associated with good solubility. Furthermore, study of the surface morphology of the obtained polymers by FE‐SEM showed that each polymers exhibit nanostructure morphology. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

DNA/lipid complex organogel with shape‐memory behavior

DNA and amphiphilic N,N,N‐trimethyl‐N‐hexadecylammonium bromide (THAB) were stoichiometrically mixed together to produce a DNA–lipid complex, which was dissolved in dimethyl sulfoxide (DMSO) at 65°C and then crosslinked with isophorone diisocyanate (IPDI). The obtained organogel swelled reversibly in DMSO, responding to the variation of temperature. Interestingly, we observed that the gel exhibited a temperature‐dependent shape‐memory behavior. Above 65°C, whatever the shape the gel was deformed to, it could retain the new shape as the temperature was decreased to room temperature, while, when the gel was heated to 65°C again, it could recover its initial shape. The shape‐memory characteristic is supposedly originated from the transition between the close‐packed and the destroyed DNA/lipid conformation. The elastic urethane crosslinking bonds between base‐pair sites act as a fixing phase. The gel holds promise in its application as a gentle actuator. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 259–263, 2002     

A super thin polytetrafluoroethylene/sulfonated poly(ether ether ketone) membrane with 91% energy efficiency and high stability for vanadium redox flow battery

In order to further decrease the cost and enhance the durability of sulfonated poly(ether ether ketone) membrane for vanadium redox flow battery, a super thin (40 μm) polytetrafluoroethylene (PTFE)/SPEEK (PS) membrane is prepared. The physico‐chemical properties and single cell performance of PS membranes prepared with different casting solvents including NMP (N‐methyl‐2‐pyrrolidone), DMF (N,N′‐dimethylformamide), and DMAc (N,N′‐dimethylacetamide) have been investigated. Results show that the energy efficiency of VRB with PS/DMF can reach up to 91.2% at the current density of 40 mA cm^?2, which is 11.1% and 6.4% higher than that of the commercial Nafion 212 and pristine SPEEK membrane, respectively. In addition, charge–discharge test over 150 times proves that the PS/DMF membrane possesses high stability and thus it is suitable for VRB application. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43593.