Ion-Conductive Poly(vinyl alcohoi)-Based IPMCs

Partially crosslinked and sulfonated poly(vinyl alcohol) (s-PVA) membranes were prepared as ion-conductive matrices of Ionic Polymer-Metal Composite (IPMC) and a new IPMC based on the s-PVA membrane was fabricated via an electroless plating procedure of platinum. PVA was reacted with sulfosuccinic acid (SSA) as a crosslinking agent with a sulfonic group and 4-(2-hydroxyethyl)piperazine-1-propanesulfonic acid (EPPS) as a side chain with a sulfonic group. The crosslinked s-PVA membranes were characterized using a FT-IR spectroscope and a scanning electron microscope-combined energy-dispersive X-ray spectrometer and were assessed in terms of water absorption, proton conductivity, and the feasibility of electroless plating, Among the prepared ionomers, the s-PVA membrane obtained at 20 wt.% SSA and 10 wt.% EPPS (S20E10 membrane) registered the highest proton conductivity of 2.9 × 10~(-2) S·m~(-1), which corresponds to one third of that of Nafion series, and only the S20E10 membrane was successfully plated via the electroless plating method without any crack and broken part. The s-PVA-based IPMC showed the one-directional displacement with 1-minute-long time-lapse comparable to typical Nafion-based IPMCs. However, the displacement under an AC potential was very limited due to its slow deformation response and the actuation performance was severely varied with actuation time including the short service life of several minutes in air. The short and variable actuation of the s-PVA-based IPMC was attributed to its large variation of surface and ionic resistances during air-operation, which is induced by the low ratio of bound to free water.     

Ion-Conductive Poly(vinyl alcohol)-Based IPMCs

Partially crosslinked and sulfonated poly(vinyl alcohol) (s-PVA) membranes were prepared as ion-conductive matrices of Ionic Polymer-Metal Composite (IPMC) and a new IPMC based on the s-PVA membrane was fabricated via an electroless plating procedure of platinum. PVA was reacted with sulfosuccinic acid (SSA) as a crosslinking agent with a sulfonic group and 4-(2-hydroxyethyl)piperazine-1-propanesulfonic acid (EPPS) as a side chain with a sulfonic group. The crosslinked s-PVA membranes were characterized using a FT-IR spectroscope and a scanning electron microscope-combined energy-dispersive X-ray spectrometer and were assessed in terms of water absorption, proton conductivity, and the feasibility of electroless plating. Among the prepared ionomers, the s-PVA membrane obtained at 20 wt.% SSA and 10 wt.% EPPS (S20E10 membrane) registered the highest proton conductivity of 2.9 × 10^?2 S·cm^?1, which corresponds to one third of that of Nafion series, and only the S20E10 membrane was successfully plated via the electroless plating method without any crack and broken part. The s-PVA-based IPMC showed the one-directional displacement with 1-minute-long time-lapse comparable to typical Nafion-based IPMCs. However, the displacement under an AC potential was very limited due to its slow deformation response and the actuation performance was severely varied with actuation time including the short service life of several minutes in air. The short and variable actuation of the s-PVA-based IPMC was attributed to its large variation of surface and ionic resistances during air-operation, which is induced by the low ratio of bound to free water.     

Verification of Beam Models for Ionic Polymer-Metal Composite Actuator

Ionic Polymer-Metal Composite (IPMC) can work as an actuator by applying a few voltages.A thick IPMC actuator,whereNafion-117 membrane was synthesized with polypyrrole/alumina composite filler,was analyzed to verify the equivalent beamand equivalent bimorph beam models.The blocking force and tip displacement of the IPMC actuator were measured with a DCpower supply and Young’s modulus of the IPMC strip was measured by bending and tensile tests respectively.The calculatedmaximum tip displacement and the Young’s modulus by the equivalent beam model were almost identical to the correspondingmeasured data.Finite element analysis with thermal analogy technique was utilized in the equivalent bimorph beam model tonumerically reproduce the force-displacement relationship of the IPMC actuator.The results by the equivalent bimorph beammodel agreed well with the force-displacement relationship acquired by the measured data.It is confirmed that the equivalentbeam and equivalent bimorph beam models are practically and effectively suitable for predicting the tip displacement,blockingforce and Young’s modulus of IPMC actuators with different thickness and different composite of ionic polymer membrane.     

Investigation of Ionic Polymer Metal Composite Actuators Loaded with Various Tetraethyl Orthosilicate Contents

Ionic Polymer Metal Composite (IPMC) can be used as an electrically activated actuator,which has been widely used in artificial muscles,bionic robotic actuators,and dynamic sensors since it has the advantages of large deformation,light weight,flexibility,and low driving voltage,etc.To further improve the mechanical properties of IPMC,this paper reports a new method for preparing organic-inorganic hybrid Nafion/SiO2 membranes.Beginning from cast Nation membranes,IPMCs with various tetraethyl orthosilicate (TEOS) contents were fabricated by electroless plating.The elastic moduli of cast Nation membranes were measured with nano indenters,the water contents were calculated,and the cross sections of Nafion membranes were observed by scanning electron microscopy.The blocking force,the displacement,and the electric current of IPMCs were then measured on a test apparatus.The results show that the blocking force increases as the TEOS content gradually increases,and that both the displacement and the electric current initially decrease,then increase.When the TEOS content is 1.5％,the IPMC shows the best improved mechanical properties.Finally,the IPMC with the best improved performance was used to successfully actuate the artificial eye and tested.     

Numerical Simulation of Dynamic Electro-Mechanical Response of Ionic Polymer-Metal Composites

Ionic Polymer-Metal Composites (IPMC) is an emerging class of Electro-Active Polymer (EAP) materials. IPMC has attractive features, such as high sensitivity and light weight, which are useful for developing novel designs in the fields of bionic actuators, artificial muscles and dynamic sensors. A Finite Element (FE) model was developed for simulating the dynamic electro-mechanical response of an IPMC structure under an external voltage input. A lumped Resistor-Capacitor (RC) model was used to describe the voltage-to-current relationship of a Nafion IPMC film for the computation of electric field intensity. Moreover, the viscoelastic property of the IPMC film was considered in the model and the non-uniform bending behavior was also taken into account. Based on the proposed model and the assumption that the thicknesses of the two electrodes are the same and uniform, the optimal coating thickness of the IPMC electrode was determined. It was demonstrated that the dynamic electro-mechanical response of the IPMC structure can be predicted by the proposed FE model, and the simulation results were in good agreement with the experimental findings.     

Advanced Electro-active Dry Adhesive Actuated by an Artificial Muscle Constructed from an Ionic Polymer Metal Composite Reinforced with Nitrogen-doped Carbon Nanocages

An advanced electro-active dry adhesive,which was composed of a mushroom-shaped fibrillar dry adhesive array actuated by an Ionic Polymer Metal Composite (IPMC) artificial muscle reinforced with nitrogen-doped carbon nanocages (NCNCs),was developed to imitate the actuation of a gecko's toe.The properties of the NCNC-reinforced Nafion membrane,the electromechanical properties of the NCNC-reinforced IPMC,and the related electro-active adhesion ability were investigated.The NCNCs were uniformly dispersed in the 0.1 wt％ NCNC/Nafion membrane,and there was a seamless connection with no clear interface between the dry adhesive and the IPMC.Our 0.1 wt％ NCNC/Nafion-IPMC actuator shows a displacement and force that are 1.6-2 times higher than those of the recast Nafion-IPMC.This is due to the increased water uptake (25.39％) and tensile strength (24.5 MPa) of the specific 3D hollow NCNC-reinforced Nafion membrane,as well as interactions between the NCNCs and the sulfonated groups of the Nafion.The NCNC/Nafion-IPMC was used to effectively actuate the mushroom-shaped dry adhesive.The normal adhesion forces were 7.85 mN,12.1 mN,and 51.7 mN at sinusoidal voltages of 1.5 V,2.5 V,and 3.5 V,respectively,at 0.1 Hz.Under the bionic leg trail,the normal and shear forces were approximately 713.5 mN (159 mN·cm-2) and 1256.6 mN (279 mN·cm-2),respectively,which satisfy the required adhesion.This new electro-active dry adhesive can be applied for active,distributed actuation and flexible grip in robots.     

Cerium Oxide Decorated Polymer Nanofibers as Effective Membrane Reinforcement for Durable,High‐Performance Fuel Cells

High‐power, durable composite fuel cell membranes are fabricated here by direct membrane deposition (DMD). Poly(vinylidene fluoride‐co ‐hexafluoropropylene) (PVDF‐HFP) nanofibers, decorated with CeO₂ nanoparticles are directly electrospun onto gas diffusion electrodes. The nanofiber mesh is impregnated by inkjet‐printed Nafion ionomer dispersion. This results in 12 µm thin multicomponent composite membranes. The nanofibers provide membrane reinforcement, whereas the attached CeO₂ nanoparticles promote improved chemical membrane durability due to their radical scavenging properties. In a 100 h accelerated stress test under hot and dry conditions, the reinforced DMD fuel cell shows a more than three times lower voltage decay rate (0.39 mV h^?1) compared to a comparably thin Gore membrane (1.36 mV h^?1). The maximum power density of the DMD fuel cell drops by 9%, compared to 54% measured for the reference. Impedance spectroscopy reveals that ionic and mass transport resistance of the DMD fuel cell are unaffected by the accelerated stress test. This is in contrast to the reference, where a 90% increase of the mass transport resistance is measured. Energy dispersive X‐ray spectroscopy reveals that no significant migration of cerium into the catalyst layers occurs during degradation. This proves that the PVDF‐HFP backbone provides strong anchoring of CeO₂ in the membrane.     

Manufacture and Performance of Ionic Polymer-Metal Composites

Ion-exchange Polymer Metal Composites （IPMC） are a new class of intelligent material that can be used effectively as actuators and artificial muscles. IPMC was fabricated and its displacement and force characteristics were investigated with respect to voltage, frequency and waveform of the controlling signal. A square waveform input generated slightly larger displacement and force than sinusoidal or triangular waveform. When the voltage was increased and the frequency was decreased, displacement and force were both increased. However, although the bending deformation of IPMC was large, the output force was much lower than we expected. Improvement of the force output is key and is the main obstacle to be overcome in order to make IPMC of practical use.     

Significantly Enhanced Actuation Performance of IPMC by Surfactant-Assisted Processable MWCNT/Nafion Composite

The performance of Ionic Polymer Metal Composite (IPMC) actuator was significantly enhanced by incorporating surfactant-assisted processable Multi-Walled Carbon Nanotubes (MWCNTs) into a Nafion solution. Cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) was employed to disperse MWCNTs in the Nafion matrix, forming a homogeneous and stable dispersion of nanotubes. The processing did not involve any strong acid treatment and thus effectively preserved the excellent electronic properties associated with MWCNT. The as-obtained MWCNT/Nafion-IPMC actuator was tested in terms of conductivity, bulk and surface morphology, blocking force and electric current. It was shown that the blocking force and the current of the new IPMC are 2.4 times and 1.67 times higher compared with a pure Nafion-based IPMC. Moreover, the MWCNT/IPMC performance is much better than previously reported Nafion-IPMC doped by acid-treated MWCNT. Such significantly improved performance should be attributed to the improvement of electrical property associated with the addition of MWCNTs without acid treatment.     

Using protein templates to direct the formation of thin-film polymer surfaces

Protein imprinted electrodes formed by the cyclic voltammetric deposition of conductive polymers, on screen-printed platinum supports, in the presence of target proteins have been fabricated. An initial layer of polypyrrole was used as a supporting polymer layer, upon which were formed two layers of polyaminophenylboronic acid. The first of these layers was non-imprinted and formed a barrier between the polypyrrole and the outer layer, which was deposited in the presence of a protein template (lysozyme or cytochrome c). After protein extraction, re-binding of the template proteins to their respective imprinted electrodes showed a distinct two-phase binding profile; whereas, binding to control polymers, made in the same way but without the addition of protein templates, showed progressive binding typical of non-specific recognition. Reductions in the observed current transmission due to bonding to the polymer surface of non-conductive protein have been used as a measure of re-binding. It was found that when challenged with 1 part per million protein in solution, the current reductions for the lysozyme and cytochrome c imprinted electrodes were 30.3 and 66.2%, respectively, compared to 4.5 and 29.9% for their respective control electrodes. All measurements carried out at -0.1 V with Ag/AgCl reference.     

An artificial muscle actuator for biomimetic underwater propulsors

In this paper, we introduce the analytical framework of the modeling dynamic characteristics of a soft artificial muscle actuator for aquatic propulsor applications. The artificial muscle used for this underwater application is an ionic polymer-metal composite (IPMC) which can generate bending motion in aquatic environments. The inputs of the model are the voltages applied to multiple IPMCs, and the output can be either the shape of the actuators or the thrust force generated from the interaction between dynamic actuator motions and surrounding water. In order to determine the relationship between the input voltages and the bending moments, the simplified RC model is used, and the mechanical beam theory is used for the bending motion of IPMC actuators. Also, the hydrodynamic forces exerted on an actuator as it moves relative to the surrounding medium or water are added to the equations of motion to study the effect of actuator bending on the thrust force generation. The proposed method can be used for modeling the general bending type artificial muscle actuator in a single or segmented form operating in the water. The segmented design has more flexibility in controlling the shape of the actuator when compared with the single form, especially in generating undulatory waves. Considering an inherent nature of large deformations in the IPMC actuator, a large deflection beam model has been developed and integrated with the electrical RC model and hydrodynamic forces to develop the state space model of the actuator system. The model was validated against existing experimental data.     

Sensor and biosensor based on Prussian Blue modified gold and platinum screen printed electrodes

Gold (Au) and platinum (Pt) screen-printed electrodes were modified with Prussian Blue (PB) for the development of amperometric sensors selective for hydrogen peroxide detection. The sensors exhibited sensitivities towards H(2)O(2) equal to 2 A M(-1) cm(-2) for Au and 1 A M(-1) cm(-2) for Pt electrodes. The sensors were also employed as the basis for construction of glucose biosensors through further modification with crystallised glucose oxidase immobilised in a Nafion membrane. In order to improve the operational stability of the modified electrodes a buffer solution containing tetrabutylammonium toluene-4-sulfonate was used. The long-term performance of the sensors and biosensors were evaluated by continuous monitoring of hydrogen peroxide and glucose solutions (50 microM and 1 mM, respectively) in the flow-injection mode for 10 h.     

Hydrophobic salt-modified Nafion for enzyme immobilization and stabilization

Over the last decade, there has been a wealth of application for immobilized and stabilized enzymes including biocatalysis, biosensors, and biofuel cells. In most bioelectrochemical applications, enzymes or organelles are immobilized onto an electrode surface with the use of some type of polymer matrix. This polymer scaffold should keep the enzymes stable and allow for the facile diffusion of molecules and ions in and out of the matrix. Most polymers used for this type of immobilization are based on polyamines or polyalcohols - polymers that mimic the natural environment of the enzymes that they encapsulate and stabilize the enzyme through hydrogen or ionic bonding. Another method for stabilizing enzymes involves the use of micelles, which contain hydrophobic regions that can encapsulate and stabilize enzymes. In particular, the Minteer group has developed a micellar polymer based on commercially available Nafion. Nafion itself is a micellar polymer that allows for the channel-assisted diffusion of protons and other small cations, but the micelles and channels are extremely small and the polymer is very acidic due to sulfonic acid side chains, which is unfavorable for enzyme immobilization. However, when Nafion is mixed with an excess of hydrophobic alkyl ammonium salts such as tetrabutylammonium bromide (TBAB), the quaternary ammonium cations replace the protons and become the counter ions to the sulfonate groups on the polymer side chains (Figure 1). This results in larger micelles and channels within the polymer that allow for the diffusion of large substrates and ions that are necessary for enzymatic function such as nicotinamide adenine dinucleotide (NAD). This modified Nafion polymer has been used to immobilize many different types of enzymes as well as mitochondria for use in biosensors and biofuel cells. This paper describes a novel procedure for making this micellar polymer enzyme immobilization membrane that can stabilize enzymes. The synthesis of the micellar enzyme immobilization membrane, the procedure for immobilizing enzymes within the membrane, and the assays for studying enzymatic specific activity of the immobilized enzyme are detailed below.     

Superacidic Electrospun Fiber‐Nafion Hybrid Proton Exchange Membranes

A novel type of hybrid membrane has been fabricated by incorporating superacidic sulfated zirconia (S‐ZrO₂) fibers into recast Nafion for proton exchange membrane fuel cells (PEMFCs). With the introduction of electrospun superacidic fiber mats, a large amount of protogenic groups aggregated in the interfacial region between S‐ZrO₂ fibers and the ionomer matrix, forming continuous pathways for facile proton transport. The resultant hybrid membranes had high proton conductivities, which were controlled by selectively adjusting the fiber diameter and fiber volume fraction. Consequently, the superacidic S‐ZrO₂ electrospun fibers are promising filler materials and hybrid membranes containing S‐ZrO₂ fiber mats can be potentially used in high‐performance fuel cells.     

Development of a micro-planar amperometric bile acid biosensor for urinalysis

The determination of bile acid concentration in urine is useful for the screening and diagnosis of various hepatobiliary diseases. Currently, there is no concise method to determine bile acid concentration in urine. This study describes a bile acid biosensor fabricated by electrochemical technique for urinalysis. The micro-planar electrodes employed for the study consisted of a working electrode (platinum), a counter electrode (platinum) and a reference electrode (silver/silver chloride (Ag/AgCl)). The sensor chip was coated with Nafion using a spin-coater in order to both eliminate many interference species in urine and achieve long-term stability of the reference electrode. Nafion coating allowed the sensor chip to prevent the electrode reaction from interference species in urine, because it is charged negative strongly (Nafion contains sulfonic acid group). Three enzymes (bile acid sulfate sulfatase: BSS, beta-hydroxysteroid dehydrogenase: beta-HSD, and NADH oxidase: NHO) were immobilized by glutaraldehyde (GA: cross-linker) onto the sensor chip, because the immobilization of enzymes by GA is simple and commonly carried out. The sensor chip was able to detect bile acid in buffer solution. The optimum enzyme ratio immobilized onto the sensor chip was BSS:beta-HSD:NHO=4:4:20 U/1 chip. There was a relationship between the concentration of bile acid and the response current value. The dynamic range of the sensor chip was 2-100 microM for bile acid. Additionally, bile acid in the urine specimen could be detected using this bile acid biosensor. We present a simple and rapid bile acid biosensor with high sensitivity and high reproducibility.     

Highly Stretchable Separator Membrane for Deformable Energy‐Storage Devices

With the emergence of stretchable electronic devices, there is growing interest in the development of deformable power accessories that can power them. To date, various approaches have been reported for replacing rigid components of typical batteries with elastic materials. Little attention, however, has been paid to stretchable separator membranes that can not only prevent internal short circuit but also provide an ionic conducting pathway between electrodes under extreme physical deformation. Herein, a poly(styrene‐b‐butadiene‐b‐styrene) (SBS) block copolymer–based stretchable separator membrane is fabricated by the nonsolvent‐induced phase separation (NIPS). The diversity of mechanical properties and porous structures can be obtained by using different polymer concentrations and tuning the affinity among major components of NIPS. The stretchable separator membrane exhibits a high stretchability of around 270% strain and porous structure having porosity of 61%. Thus, its potential application as a stretchable separator membrane for deformable energy devices is demonstrated by applying to organic/aqueous electrolyte–based rechargeable lithium‐ion batteries. As a result, these batteries manifest good cycle life and stable capacity retention even under a stretching condition of 100%, without compromising the battery's performance.     

Biomimetic robotic Venus flytrap (Dionaea muscipula Ellis) made with ionic polymer metal composites

The work described in this paper is a novel design of a robotic Venus flytrap (VFT) (Dionaea muscipula Ellis) by means of ionic polymeric metal composite (IPMC) artificial muscles as distributed nanosensors and nanoactuators. Rapid muscular movements in carnivorous plants, such as VFT, which are triggered by antenna-like sensors (trigger hair), present a golden key to study distributed biomolecular motors. Carnivorous plants, such as VFT, possess built-in intelligence (trigger hairs), as a strategy to capture prey, that can be turned on in a controlled manner. In the case of the VFT, the prey that is lured by the sweet nectar in the VFT pair of jaw-like lobes has to flip and move the trigger hairs, which are colorless, bristle-like and pointed. The dynamically moved trigger hairs then electro-elastically send an electric signal to the internal ions in the lobe to migrate outwardly for the jaw-like lobes to close rapidly to capture the prey. The manner in which the VFT lobes bend inward to capture the prey shows a remarkable similarity with typical IPMCs bending in an electric field. Furthermore, the mechano-electrical sensing characteristics of IPMCs also show a remarkable resemblance to mechano-electrical trigger hairs on the lobes of the VFT. The reader is referred to a number of papers in connection with sensing and actuation of IPMCs in particular. Thus, one can integrate IPMC lobes with a common electrode in the middle of one end of the lobes to act like a spine and use IPMC bristles as trigger finger to sense the intrusion of a fly or insect to send a sensing signal to a solid state relay which then triggers the actuation circuit of the IPMC lobes to rapidly bend toward each other and close. The two lobes, which form the trap, are attached to the midrib common electrode which is conveniently termed the spine. The upper surface of each lobe is dished, and spaced along the free margins of the lobes with some 15-20 prong-like teeth. These are tough and pointed, and are inclined at an inward angle so that when the trap is sprung shut they will interlock. We have been experimenting with the VFT closing of its jaw-like lobes that close in about 0.3 s and have gained a lot of knowledge to report on the ionic and electrical mechanisms involved in the operation of such intelligent distributed biomolecular motors.     

Silicon Composite Electrodes with Dynamic Ionic Bonding

Silicon (Si) composite electrodes are developed with increased cycle lifetimes and reliability through dynamic ionic bonding between active Si nanoparticles and a polymer binder. Amine groups are covalently attached to Si nanoparticles via surface functionalization. Si composite electrodes are fabricated by combining the Si nanoparticles with a poly(acrylic acid) (PAA) binder. The formation of ionic bonds between amine groups on Si particles and carboxylic acid groups on the PAA binder is characterized by X‐ray photoelectron spectroscopy and Raman spectroscopy. Si composite anodes with ionic bonding demonstrate long term cycling stability with capacity retention of 80% at 400 cycles at a current density of 2.1 A g^?1 and good rate capability. The dynamic ionic bonds effectively mitigate the deterioration of electrical interfaces in the composite anodes as suggested by stable impedance over 300 cycles.     

Miniaturized pH biosensors based on electrochemically modified electrodes with biocompatible polymers

Potentiometric pH sensors based on linear polyethylenimine (L-PEI) and linear polypropylenimine(L-PPI), two synthetic enzymes and biocompatible polymers, films were prepared by electropolymerization of three different monomers: ethylenediamine (EDA), 1,3-diaminopropane (1,3-DAP) and diethylenetriamine (DETA) in order to be used in clinical, dermatological and biological applications, such as in vivo analysis. In a first step a biosensor was tested which consisted in a platinum wire protruded from glass sheath. The polymer film coated on these platinum electrodes showed good linear potentiometric responses to pH changes from pH 3 to 10. Resulting electrodes present both good reversibility and good stability versus time. The effect of the different polymer film thicknesses to potentiometric responses was also studied. This study allowed us to develop a miniaturized pH biosensor in the second step. This sensor was fabricated using photo-lithography, followed by sputtering and lift-off processes, and it included an electronic detection system. We have also successfully studied the potentiometric responses to pH changes of this device over a period of 1 month, and so we propose this new pH micro-biosensor as an alternative to classical pH sensors currently used in dermatology.     

In vivo calibration of the subcutaneous amperometric glucose sensors using a non-enzyme electrode

A new two-point calibration method for the subcutaneous amperometric continuous glucose sensor is reported. The proposed method is based on direct measurement of the background current (I(o)) using a non-enzyme electrode. For in vivo test, three electrodes were implanted in rabbits. Two of the three were identical needle-type enzyme electrodes with perfluorinated polymer outer layers (Pt/enzyme layer/Kel-F/PTFE/Kel-F/Nafion) that were placed in subcutaneous tissue and in a vessel (ear artery), respectively. And one non-enzyme electrode with exactly the same membrane composition as those of other two was in the subcutaneous layer to measure the background current. Implantation in the subcutaneous layer generated many crevices on the protecting layers of the electrodes. The signals from enzyme electrodes were effectively corrected by the measured background current from the non-enzyme electrode. In addition, a telemetric monitoring system was developed and evaluated for in vivo continuous glucose monitoring in order to alleviate the problems of motion artifact.