Prestrain‐Free Dielectric Elastomers Based on Acrylic Thermoplastic Elastomer Gels: A Morphological and (Electro)Mechanical Property Study

Recent efforts have established that thermoplastic elastomer gels (TPEGs) composed of styrenic triblock copolymers swollen with a midblock‐selective solvent exhibit remarkable electromechanical properties as high‐performance dielectric elastomers. This class of electroactive polymers typically requires high electric fields for actuation, and a shortcoming that continues to thwart the widespread commercialization of such materials in general is the need to apply mechanical prestrain prior to electroactuation to decrease film thickness and, thus, the electric potential required to promote actuation. To alleviate this requirement, TPEGs consisting of acrylic triblock copolymers differing in molecular weight and composition, and swollen with a high dielectric, midblock‐selective solvent are investigated. Synchrotron small‐angle x‐ray scattering is used to probe the nanoscale morphologies of the resultant materials, and analysis of quasi‐static and cyclic tensile properties provides additional insight into both blend morphologies and electroactuation efficacy. Actuation strains measured in the absence of mechanical prestrain exceed 100% on an area basis, and electric fields capable of inducing actuation are as low as ～20 kV/mm. Failure occurs by either electromechanical instability or dielectric breakdown, depending on the copolymer and TPEG composition employed. The electromechanical properties of these acrylic‐based TPEGs match or exceed those of skeletal muscle, in which case they constitute an attractive and unexplored alternative to existing dielectric elastomers.     

A General Strategy to Disperse and Functionalize Carbon Nanotubes Using Conjugated Block Copolymers

A general strategy to disperse and functionalize pristine carbon nanotubes in a single‐step process is developed using conjugated block copolymers. The conjugated block copolymer contains two blocks: a conjugated polymer block of poly(3‐hexylthiophene), and a functional non‐conjugated block with tunable composition. When the pristine carbon nanotubes are sonicated with the conjugated block copolymers, the poly(3‐hexylthiophene) blocks bind to the surface of de‐bundled carbon nanotubes through non‐covalent π–π interactions, stabilizing the carbon nanotube dispersion, while the functional blocks locate at the outer surface of carbon nanotubes, rendering the carbon nanotubes with desired functionality. In this paper, conjugated block copolymers of poly(3‐hexylthiophene)‐b‐poly(methyl methacrylate), poly(3‐hexylthiophene)‐b‐poly(acrylic acid), and poly(3‐hexylthiophene)‐b‐poly(poly(ethylene glycol) acrylate) are used to demonstrate this general strategy.     

New Silicone Composites for Dielectric Elastomer Actuator Applications In Competition with Acrylic Foil

Several polydimethylsiloxane elastomers were developed and investigated regarding their potential use as materials in dielectric elastomer actuators (DEA). A hydroxyl end‐functionalized polydimethylsiloxane was reacted with different crosslinkers and the electromechanical properties of the resulting elastomers were investigated. The silicone showing the best actuation at the lowest electric field was further used as matrix and compounded with encapsulated conductive polyaniline particles. These composites have enhanced properties including increased strain at break, higher dielectric constant as well as, gratifyingly, breakdown fields higher than that of the matrix. One of the newly synthesized composites is compared to the commercially available acrylic foil VHB 4905 (3M) which is currently the most commonly used elastomer for DEA applications. It was found that this material has little hysteresis and can be activated at lower voltages compared to VHB 4905. For example, when the newly synthesized composite was 30% prestrained, a lateral actuation strain of about 12% at 40 V μm^?1 was measured while half of this actuation strain at the same voltage was measured for VHB 4905 film that was 300% prestrained. It also survived more than 100 000 cycles at voltages which are close to the breakdown field. Such materials might find applications wherever small forces but large strains at low voltages are required, in, for example, tactile displays.     

Electric Actuation of Nanostructured Thermoplastic Elastomer Gels with Ultralarge Electrostriction Coefficients

Electrostriction facilitates the electric field‐stimulated mechanical actuation of dielectric materials. This work demonstrates that introduction of dielectric mismatched nanodomains to a dielectric elastomer results in an unexpected ultralarge electrostriction coefficient, enabling a large electromechanical strain response at a low electric field. This strong electrostrictive effect is attributed to the development of an inhomogeneous electric field across the film thickness due to the high density of interfaces between dielectric mismatched periodic nanoscale domains. The periodic nanostructure of the nanostructured gel also makes it possible to measure the true electromechanical strain from the dimensional change monitored via in situ synchrotron small angle X‐ray scattering. The work offers a promising pathway to design novel high performance dielectric elastomers as well as to understand the underlying operational mechanism of nanostructured multiphase electrostrictive systems.     

Intramolecular Donor–Acceptor Regioregular Poly(3‐hexylthiophene)s Presenting Octylphenanthrenyl‐Imidazole Moieties Exhibit Enhanced Charge Transfer for Heterojunction Solar Cell Applications

Intramolecular donor–acceptor structures prepared by covalently binding conjugated octylphenanthrenyl‐imidazole moieties onto the side chains of regioregular poly(3‐hexylthiophene)s exhibit lowered bandgaps and enhanced electron transfer compared to the parent polymer, e.g., conjugation of 90 mol% octylphenanthrenyl‐imidazole moieties onto poly(3‐hexylthiophene) chains reduces the optical bandgap from 1.91 to 1.80 eV, and the electron transfer probability is at least twice as high as that of pure poly(3‐hexylthiophene) when blended with [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester. The lowered bandgap and the fast charge transfer both contribute to much higher external quantum efficiencies, thus much higher short‐circuit current densities for copolymers presenting octylphenanthrenyl‐imidazole moieties, relative to those of pure poly(3‐hexylthiophene)s. The short‐circuit current density of a device prepared from a copolymer presenting 90 mol% octylphenanthrenyl‐imidazole moieties is 13.7 mA · cm^?2 which is an increase of 65% compared to the 8.3 mA · cm^?2 observable for a device containing pure poly(3‐hexylthiophene). The maximum power conversion efficiency of this particular copolymer is 3.45% which suggest that such copolymers are promising polymeric photovoltaic materials.     

Electrostatic Self‐Assembly Conjugated Polyelectrolyte‐Surfactant Complex as an Interlayer for High Performance Polymer Solar Cells

A simple method is demonstrated to improve the film‐forming properties and air stability of a conjugated polyelectrolyte (CPE) without complicated synthesis of new chemical structures. An anionic surfactant, sodium dodecybenzenesulfonate (SDS), is mixed with cationic CPEs. The electrostatic attraction between these two oppositely‐charged materials provides the driving force to form a stable CPE‐surfactant complex. Compared with a pure CPE, this electrostatic complex is not only compatible with highly hydrophobic bulk‐heterojunction (BHJ) films, e.g. poly(3‐hexylthiophene):[6,6]‐phenyl C₆₁ butyric acid methyl ester (P3HT:PCBM), but also works well with other low bandgap polymer‐based BHJ films. Using this complex as a cathode interface layer, a high power conversion efficiency of 4% can be obtained in P3HT:PCBM solar cells together with improved stability in air. Moreover, ～20% performance enhancement can also be achieved when the complex is used as an interlayer to replace calcium metal for low bandgap polymer‐based BHJ systems.     

Stimulating Acrylic Elastomers by a Triboelectric Nanogenerator – Toward Self‐Powered Electronic Skin and Artificial Muscle

Dielectric elastomers are a type of actuator materials that exhibit excellent performance as artificial muscles, but a high driving voltage is required for their operation. By using the amazingly high output voltage generated from a triboelectric nanogenerator (TENG), a thin film dielectric elastomer actuator (DEA) can be directly driven by the contact‐separation motion of TENG, demonstrating a self‐powered actuation system. A TENG with a tribo surface area of 100 cm² can induce an expansion strain of 14.5% for the DEA samples (electrode diameter of 0.6 cm) when the system works stably within the contact‐separation velocity ranging from 0.1 to 10 cm s^?1. Finally, two simple prototypes of an intelligent switch and a self‐powered clamper based on the TENG and DEA are demonstrated. These results prove that the dielectric elastomer is an ideal material to work together with TENG and thereby the fabricated actuation system can potentially be applied to the field of electronic skin and soft robotics.     

High Breakdown Field Dielectric Elastomer Actuators Using Encapsulated Polyaniline as High Dielectric Constant Filler

A novel method allowing rapid production of reliable composites with increased dielectric constant and high dielectric strength for dielectric elastomer actuators (DEA) is reported. The promising approach using composites of conductive particles and insulating polymers generally suffers from low breakdown fields when applied to DEA devices. The present publication shows how to overcome this deficiency by using conductive polyaniline (PANI) particles encapsulated into an insulating polymer shell prior to dispersion. PANI particles are encapsulated using miniemulsion polymerization (MP) of divinylbenzene (DVB). The encapsulation process is scaled up to approximately 20 g particles per batch. The resulting particles are used as high dielectric constant (?′) fillers. Composites in a polydimethylsiloxane (PDMS) matrix are prepared and the resulting films characterized by dielectric spectroscopy and tensile tests, and evaluated in electromechanical actuators. The composite films show a more than threefold increase in ?′, breakdown field strengths above 50 V μm^?1, and increased strain at break. These novel materials allow tuning the actuation strain or stress output and have potential as materials for energy harvesting.     

Impedance Measurements as a Simple Tool to Control the Quality of Conjugated Polymers Designed for Photovoltaic Applications

The problem of batch‐to‐batch variation of electronic properties and purity of conjugated polymers used as electron donor and photon harvesting materials in organic solar cells is addressed. A simple method is developed for rapid analysis of electronic quality of polymer‐based materials. It is shown that appearance of impurities capable of charge trapping changes electrophysical properties of conjugated polymers. In particular, a clear correlation between the effective relaxation time τeff and relative photovoltaic performance (η/η_max) is revealed for samples of poly(3‐hexylthiophene) intentionally polluted with a palladium catalyst. This dependence is also valid for all other investigated samples of conjugated polymers. Therefore, fast impedance measurements at three different frequencies allow one to draw conclusions about the purity of the analyzed polymer sample and even estimate its photovoltaic performance. The developed method might find extensive applications as a simple tool for product quality control in the laboratory and industrial‐scale production of conjugated polymers for electronic applications.     

Superstretchable,Self‐Healing Polymeric Elastomers with Tunable Properties

Utilization of self‐healing chemistry to develop synthetic polymer materials that can heal themselves with restored mechanical performance and functionality is of great interest. Self‐healable polymer elastomers with tunable mechanical properties are especially attractive for a variety of applications. Herein, a series of urea functionalized poly(dimethyl siloxane)‐based elastomers (U‐PDMS‐Es) are reported with extremely high stretchability, self‐healing mechanical properties, and recoverable gas‐separation performance. Tailoring the molecular weights of poly(dimethyl siloxane) or weight ratio of elastic cross‐linker offers tunable mechanical properties of the obtained U‐PDMS‐Es, such as ultimate elongation (from 984% to 5600%), Young's modulus, ultimate tensile strength, toughness, and elastic recovery. The U‐PDMS‐Es can serve as excellent acoustic and vibration damping materials over a broad range of temperature (over 100 °C). The strain‐dependent elastic recovery behavior of U‐PDMS‐Es is also studied. After mechanical damage, the U‐PDMS‐Es can be healed in 120 min at ambient temperature or in 20 min at 40 °C with completely restored mechanical performance. The U‐PDMS‐Es are also demonstrated to exhibit recoverable gas‐separation functionality with retained permeability/selectivity after being damaged.     

Electrical and Mechanical Self‐Healing in High‐Performance Dielectric Elastomer Actuator Materials

Dielectric elastomers are of interest for actuator applications due to their large actuation strain, high bandwidth, high energy density, and their flexible nature. If future dielectric elastomers are to be used reliably in applications that include soft robotics, medical devices, artificial muscles, and electronic skins, there is a need to design devices that are tolerant to electrical and mechanical damage. In this paper, the first report of self‐healing of both electrical breakdown and mechanical damage in dielectric actuators using a thermoplastic methyl thioglycolate–modified styrene–butadiene–styrene (MGSBS) elastomer is provided. The self‐healing functions are examined from the material to device level by detailed examination of the healing process, and characterization of electrical properties and actuator response before and after healing. It is demonstrated that after dielectric breakdown, the initial dielectric strength can be recovered by up to 67%, and after mechanical damage, a 39% recovery can be achieved with no degradation of the strain–voltage response of the actuators. The elastomer can also heal a combination of mechanical and electrical failures. This work provides a route to create robust and damage tolerant dielectric elastomers for soft robotic and other applications related to actuator and energy‐harvesting systems.     

Synergistic Improvement of Actuation Properties with Compatibilized High Permittivity Filler

Electroactive polymers can be used for actuators with many desirable features, including high electromechanical energy density, low weight, compactness, direct voltage control, and complete silence during actuation. These features may enable personalized robotics with much higher ability to delicately manipulate their surroundings than can be achieved with currently available actuators; however, much work is still necessary to enhance the electroactive materials. Electric field‐driven actuator materials are improved by an increase in permittivity and by a reduction in stiffness. Here, a synergistic enhancement method based on a macromolecular plasticizing filler molecule with a combination of both high dipole moment and compatibilizer moieties, synthesized to simultaneously ensure improvement of electromechanical properties and compatibility with the host matrix is presented. Measurements show an 85% increase in permittivity combined with 290% reduction in mechanical stiffness. NMR measurements confirm the structure of the filler while DSC measurements confirm that it is compatible with the host matrix at all the mixture ratios investigated. Actuation strain measurements in the pure shear configuration display an increase in sensitivity to the electrical field of more than 450%, confirming that the filler molecule does not only improve dielectric and mechanical properties, it also leads to a synergistic enhancement of actuation properties by simple means.     

Photocrosslinkable Polythiophenes for Efficient,Thermally Stable,Organic Photovoltaics

Photocrosslinkable bromine‐functionalized poly(3‐hexylthiophene) (P3HT‐Br) copolymers designed for application in solution‐processed organic photovoltaics are prepared by copolymerization of 2‐bromo‐3‐(6‐bromohexyl) thiophene and 2‐bromo‐3‐hexylthiophene. The monomer ratio is carefully controlled to achieve a UV photocrosslinkable layer while retaining the π–π stacking feature of the conjugated polymers. The new materials are used as electron donors in both bulk heterojunction (BHJ) and bilayer type photovoltaic devices. Unlike devices prepared from either P3HT:PCBM blend or P3HT‐Br:PCBM blend without UV treatment, photocrosslinked P3HT‐Br:PCBM devices are stable even when annealed for two days at the elevated temperature of 150 °C as the nanophase separated morphology of the bulk heterojunction is stabilized as confirmed by optical microscopy and grazing incidence wide angle X‐ray scattering (GIWAXS). When applied to solution‐processed bilayer devices, the photocrosslinkable materials show high power conversion efficiencies (～2%) and excellent thermal stability (3 days at 150 °C). Such performance, one of the highest obtained for a bilayer device fabricated by solution processing, is achieved as crosslinking does not disturb the π–π stacking of the polymer as confirmed by GIWAXS measurements. These novel photocrosslinkable materials provide ready access to efficient bilayer devices thus enabling the fundamental study of photophysical characteristics, charge generation, and transport across a well‐defined interface.     

Intrinsic Surface Dipoles Control the Energy Levels of Conjugated Polymers

Conjugated polymers are an important class of materials for organic electronics applications. There, the relative alignment of the electronic energy levels at ubiquitous organic/(in)organic interfaces is known to crucially impact device performance. On the prototypical example of poly(3‐hexylthiophene) and a fluorinated derivative, the energies of the ionization and affinity levels of π‐conjugated polymers are revealed to critically depend on the orientation of the polymer backbones with respect to such interfaces. Based on extensive first‐principles calculations, an intuitive electrostatic model is developed that quantitatively traces these observations back to intrinsic intramolecular surface dipoles arising from the π‐electron system and intramolecular polar bonds. The results shed new light on the working principles of organic electronic devices and suggest novel strategies for materials design.     

Improved Performance of Polymer:Polymer Solar Cells by Doping Electron‐Accepting Polymers with an Organosulfonic Acid

The performance of polymer:polymer solar cells that are made using blend films of poly(3‐hexylthiophene) (P3HT) and poly(9,9‐dioctylfluorene‐co‐ benzothiadiazole (F8BT) is improved by doping the F8BT polymer with an organosulfonic acid [4‐ethylbezenesulfonic acid (EBSA)]. The EBSA doping of F8BT, to form F8BT‐EBSA, is performed by means of a two‐stage reaction at room temperature and 60°C with various EBSA weight ratios. The X‐ray photoelectron spectroscopy measurement reveals that both sulfur and nitrogen atoms in the F8BT polymer are affected by the EBSA doping. The F8BT‐EBSA films exhibit huge photoluminescence quenching, ionization potential shift toward lower energy, and greatly enhanced electron mobility. The short‐circuit current density of solar cells is improved by ca. twofold (10 wt.% EBSA doping), while the open‐circuit voltage increases by ca. 0.4 V. Consequently, the power conversion efficiency was improved by ca. threefold, even though the optical density of the P3HT:F8BT‐EBSA blend film is reduced by 10 wt.% EBSA doping due to the nanostructure and surface morphology change.     

Effects of Postproduction Treatment on Plastic Solar Cells

Efficiencies of organic solar cells based on an interpenetrating network of a conjugated polymer and a fullerene as donor and acceptor materials still need to be improved for commercial use. We have developed a postproduction treatment that improves the performance of solar cells based on poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) by means of a tempering cycle at elevated temperatures in which an external voltage is simultaneously applied, resulting in a significant increase of the short‐circuit current. Using this postproduction treatment, an enhancement of the short‐circuit current density, I_sc, to 8.5 mA cm^–2 under illumination with white light at an illumination intensity of 800 W m^–2 and an increase in external quantum efficiency (IPCE, incident photon to collected electron efficiency) to 70 % are demonstrated.     

Strain‐Responsive Polyurethane/PEDOT:PSS Elastomeric Composite Fibers with High Electrical Conductivity

It is a challenge to retain the high stretchability of an elastomer when used in polymer composites. Likewise, the high conductivity of organic conductors is typically compromised when used as filler in composite systems. Here, it is possible to achieve elastomeric fiber composites with high electrical conductivity at relatively low loading of the conductor and, more importantly, to attain mechanical properties that are useful in strain‐sensing applications. The preparation of homogenous composite formulations from poly­urethane (PU) and poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) that are also processable by fiber wet‐spinning techniques are systematically evaluated. With increasing PEDOT:PSS loading in the fiber composites, the Young's modulus increases exponentially and the yield stress increases linearly. A model describing the effects of the reversible and irreversible deformations as a result of the re‐arrangement of PEDOT:PSS filler networks within PU and how this relates to the electromechanical properties of the fibers during the tensile and cyclic stretching is presented.     

3D Printing of Interdigitated Dielectric Elastomer Actuators

Dielectric elastomer actuators (DEAs) are soft electromechanical devices that exhibit large energy densities and fast actuation rates. They are typically produced by planar methods and, thus, expand in‐plane when actuated. Here, reported is a method for fabricating 3D interdigitated DEAs that exhibit in‐plane contractile actuation modes. First, a conductive elastomer ink is created with the desired rheology needed for printing high‐fidelity, interdigitated electrodes. Upon curing, the electrodes are then encapsulated in a self‐healing dielectric matrix composed of a plasticized, chemically crosslinked polyurethane acrylate. 3D DEA devices are fabricated with tunable mechanical properties that exhibit breakdown fields of 25 V µm^?1 and actuation strains of up to 9%. As exemplars, printed are prestrain‐free rotational actuators and multi‐voxel DEAs with orthogonal actuation directions in large‐area, out‐of‐plane motifs.     

The Interesting Influence of Nanosprings on the Viscoelasticity of Elastomeric Polymer Materials: Simulation and Experiment

Among all carbon nanostructured materials, helical nanosprings or nanocoils have attracted particular interest as a result of their special mechanical behavior. Here, carbon nanosprings are used to adjust the viscoelasticity and reduce the resulting hysteresis loss (HL) of elastomeric polymer materials. Two types of nanospring‐filled elastomer composites are constructed as follows: system I is obtained by directly blending polymer chains with nanosprings; system II is composed of the self‐assembly of a tri‐block structure such as chain‐nanospring‐chain. Coarse‐grained molecular dynamics simulations show that the incorporation of nanosprings can improve the mechanical strength of the elastomer matrix through nanoreinforcement and considerably decrease the hysteresis loss. This finding is significant for reducing fuel consumption and improving fuel efficiency in the automobile tire industry. Furthermore, it is revealed that the spring constant of nanosprings and the interfacial chemical coupling between chains and nanosprings both play crucial roles in adjusting the viscoelasticity of elastomers. It is inferred that elastomer/carbon nanostructured materials with good flexibility and reversible mechanical response (carbon nanosprings, nanocoils, nanorings, and thin graphene sheets) have both excellent mechanical and low HL properties; this may open a new avenue for fabrication of high performance automobile tires and facilitate the large‐scale industrial application of these materials.     

Spectroscopic Evaluation of Mixing and Crystallinity of Fullerenes in Bulk Heterojunctions

The microstructure of blend films of conjugated polymer and fullerene, especially the degree of mixing and crystallization, impacts the performance of organic photovoltaic devices considerably. Mixing and crystallization affect device performance in different ways. These phenomena are not easy to screen using traditional methods such as imaging. In this paper, the amorphous regiorandom poly(3‐hexylthiophene) is blended with the potentially crystalline fullerene [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester PCBM and the amorphous bis‐adduct. First, the degree of mixing of polymer: fullerene blends is evaluated using UV–Vis absorption, steady‐state and ultra‐fast photoluminescence spectroscopy. The blue‐shift of the polymer emission and absorption onset are used in combination with the saturation of the polymer emission decay time upon fullerene addition in order to infer the onset of aggregation of the blends. Second, the crystallinity of the fullerene is probed using variable angle spectroscopic ellipsometry (VASE), electroluminescence and photoluminescence spectroscopy. It is shown that the red‐shift of charge transfer emission in the case of PCBM based blends cannot be explained solely by a variation of optical dielectric constant as probed by VASE. A combination of optical spectroscopy techniques, therefore, allows to probe the degree of mixing and can also distinguish between aggregation and crystallization of fullerenes.