Green and Blue Electrochromic Polymers from Processable Siloxane Precursors

Herein we report the synthesis of a new class of processable siloxane precursor polymers consisting of aromatic groups and flexible siloxane linkages and their conversions to green and blue electrochromic polymers in the solid state. 3,4-Ethylenedioxythiophene (EDOT), 2,2′-bis­(3,4-ethylenedioxythiophene) (BiEDOT), and a donor–acceptor moiety 4,7-bis­(EDOT)-2,1,3-benzothiadiazole (BEBTD) were incorporated as aromatic groups to demonstrate the versatility of the precursor method to different aromatic systems. The utilization of a siloxane linkage allows for a precursor polymer exhibiting improved solubility in common organic solvents and accessible glass transition temperatures (−1 to 132 °C) as compared to a previously reported silane precursor. A simple method to control the thermal properties of the precursor was also demonstrated by incorporation of both siloxane and silane functionalities into the precursor backbone. The oxidatively converted product from the precursors showed electronic and optoelectronic properties comparable to the conjugated polymer prepared by conventional electrochemical polymerization of monomers in an electrolyte bath. In addition to the dark-blue to sky-blue electrochromic PEDOT from EDOT and BiEDOT, a dual-band absorbing green to sky-blue electrochromic polymer was demonstrated using BEBTD. This demonstrates that the precursor approach is easily applicable and feasible for the preparation of conjugated polymers from numerable electrochemically polymerizable aromatic groups

PEDOT:PSS “Wires” Printed on Textile for Wearable Electronics

Herein, the fabrication of all-organic conductive wires is demonstrated by utilizing patterning techniques such as inkjet printing and sponge stencil to apply poly­(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT:PSS) onto nonwoven polyethylene terephthalate (PET) fabric. The coating of the conducting polymer is only present on the surface of the substrate (penetration depth ∼ 200 μm) to retain the functionality and wearability of the textile. The wires fabricated by different patterning techniques provide a wide range of resistance, i.e., tens of kΩ/□ to less than 2 Ω/□ that allows the resistance to be tailored to a specific application. The sheet resistance is measured to be as low as 1.6 Ω/□, and the breakdown current is as high as 0.37 A for a 1 mm wide line. The specific breakdown current exceeds the previously reported values of macroscopic carbon nanotube based materials. Simple circuits composed of the printed wires are demonstrated, and resistance of the circuit from the measurement agrees with the calculated value based on Kirchhoff’s rules. Additionally, the printed PEDOT:PSS wires show less than 6.2% change in sheet resistance after three washing and drying cycles using detergent

Rationally Designed Polyimides for High-Energy Density Capacitor Applications

Development of new dielectric materials is of great importance for a wide range of applications for modern electronics and electrical power systems. The state-of-the-art polymer dielectric is a biaxially oriented polypropylene (BOPP) film having a maximal energy density of 5 J<b>/</b>cm³ and a high breakdown field of 700 MV/m, but with a limited dielectric constant (∼2.2) and a reduced breakdown strength above 85 °C. Great effort has been put into exploring other materials to fulfill the demand of continuous miniaturization and improved functionality. In this work, a series of polyimides were investigated as potential polymer materials for this application. Polyimide with high dielectric constants of up to 7.8 that exhibits low dissipation factors (<1%) and high energy density around 15 J<b>/</b>cm³, which is 3 times that of BOPP, was prepared. Our syntheses were guided by high-throughput density functional theory calculations for rational design in terms of a high dielectric constant and band gap. Correlations of experimental and theoretical results through judicious variations of polyimide structures allowed for a clear demonstration of the relationship between chemical functionalities and dielectric properties

Screen-Printed PEDOT:PSS Electrodes on Commercial Finished Textiles for Electrocardiography

Electrocardiography (ECG) is an essential technique for analyzing and monitoring cardiovascular physiological conditions such as arrhythmia. This article demonstrates the integration of screen-printed ECG circuitry from a commercially available conducting polymer, PEDOT:PSS, onto commercially available finished textiles. ECG signals were recorded in dry skin conditions due to the ability of PEDOT:PSS to function as both ionic and electronic conductors. The signal amplifies when the skin transpires water vapor or by applying a common lotion on the skin. Finally, PEDOT:PSS wires connected to PEDOT:PSS electrodes have been shown to record ECG signals comparable to Ag/AgCl connected to copper wires

Optimization of Organotin Polymers for Dielectric Applications

Recently, there has been a growing interest in developing wide band gap dielectric materials as the next generation insulators for capacitors, photovoltaic devices, and transistors. Organotin polyesters have shown promise as high dielectric constant, low loss, and high band gap materials. Guided by first-principles calculations from density functional theory (DFT), in line with the emerging codesign concept, the polymer poly­(dimethyltin 3,3-dimethylglutarate), p­(DMTDMG), was identified as a promising candidate for dielectric applications. Blends and copolymers of poly­(dimethyltin suberate), p­(DMTSub), and p­(DMTDMG) were compared using increasing amounts of p­(DMTSub) from 10% to 50% to find a balance between electronic properties and film morphology. DFT calculations were used to gain further insight into the structural and electronic differences between p­(DMTSub) and p­(DMTDMG). Both blend and copolymer systems showed improved results over the homopolymers with the films having dielectric constants of 6.8 and 6.7 at 10 kHz with losses of 1% and 2% for the blend and copolymer systems, respectively. The energy density of the film measured as a <i>D</i>–<i>E</i> hysteresis loop was 6 J/cc for the copolymer, showing an improvement compared to 4 J/cc for the blend. This improvement is hypothesized to come from a more uniform distribution of diacid repeat units in the copolymer compared to the blend, leading toward improved film quality and subsequently higher energy density

Acrylated Poly(3,4-propylenedioxythiophene) for Enhancement of Lifetime and Optical Properties for Single-Layer Electrochromic Devices

We utilized our in situ method for the one-step assembly of single-layer electrochromic devices (ECDs) with a 3,4-propylenedioxythiophene (ProDOT) acrylate derivative, and long-term stability was achieved. By coupling the electroactive monomer to the cross-linkable polymer matrix, preparation of the electrochromic ProDOT polymer can occur followed by UV cross-linking. Thus, we achieve immobilization of the unreacted monomer, which prevents any degradative processes from occurring at the counter electrode. This approach eliminated spot formation in the device and increased stability to over 10 000 cycles when compared to 500 cycles with conventional ProDOT devices wherein the monomer is not immobilized. The acrylated electrochromic polymer exhibits similar electrochromic properties as conventional ProDOT devices, such as photopic contrast (48% compared to 46%) and switch speed (both 2 s). This method can be applied to any one-layer electrochromic system where improved stability is desired

Rational Design of Organotin Polyesters

Large dielectric constant and band gap are essential for insulating materials used in applications such as capacitors, transistors and photovoltaics. Of the most common polymers utilized for these applications, polyvinyldiene fluoride (PVDF) offers a good balance between dielectric constant, >10, and band gap, 6 eV, but suffers from being a ferroelectric material. Herein, we investigate a series of aliphatic organotin polymers, p­[DMT­(CH₂)<i>_n</i>], to increase the dipolar and ionic part of the dielectric constant while maintaining a large band gap. We model these polymers by performing first-principles calculations based on density functional theory (DFT), to predict their structures, electronic and total dielectric constants and energy band gaps. The modeling and experimental values show strong correlation, in which the polymers exhibit both high dielectric constant, ≥5.3, and large band gap, ≥4.7 eV with one polymer displaying a dielectric constant of 6.6 and band gap of 6.7 eV. From our work, we can identify the ideal amount of tin loading within a polymer chain to optimize the material for specific applications. We also suggest that the recently developed modeling methods based on DFT are efficient in studying and designing new generations of polymeric dielectric materials

Poly(cannabinoid)s: Hemp-Derived Biocompatible Thermoplastic Polyesters with Inherent Antioxidant Properties

The legalization of hemp cultivation in the United States has caused the price of hemp-derived cannabinoids to decrease 10-fold within 2 years. Cannabidiol (CBD), one of many naturally occurring diols found in hemp, can be purified in high yield for low cost, making it an interesting candidate for polymer feedstock. In this study, two polyesters were synthesized from the condensation of either CBD or cannabigerol (CBG) with adipoyl chloride. Poly(CBD-Adipate) was cast into free-standing films and subjected to thermal, mechanical, and biological characterization. Poly(CBD-Adipate) films exhibited a lack of cytotoxicity toward adipose-derived stem cells while displaying an inherent antioxidant activity compared to poly(lactide) films. Additionally, this material was found to be semi-crystalline and able to be melt-processed into a plastic hemp leaf using a silicone baking mold