The glass transition temperature (T g ) of a conjugated polymer can be used to predict its morphological stability and mechanical properties. Despite the importance of this parameter in applications from organic solar cells to wearable electronics, it is not easy to measure. The T g is often too weak to detect using conventional differential scanning calorimetry (DSC). Alternative methodse.g., variable temperature ellipsometryrequire specialized equipment. This paper describes a technique for measuring the T g of thin films of semicrystalline conjugated polymers using only a hot plate and an ultraviolet−visible (UV−vis) spectrometer. UV−vis spectroscopy is used to measure changes in the absorption spectrum due to molecular-scale rearrangement of polymers when heated past T g , corresponding to the onset of the formation of photophysical aggregates. A deviation metric, defined as the sum of the squared deviation in absorbance between as-cast and annealed films, is used to quantify shifts in the absorption spectra. The glass transition is observed as a change in slope in a plot of the deviation metric versus temperature. To demonstrate the usefulness of this technique, a variety of semiconducting polymers are tested: P3BT, PBTTT-C14, F8BT, PDTSTPD, PTB7, PCDTBT, TQ1, and MEH-PPV. These polymers represent a range of solid-state morphologies, from highly ordered to predominantly amorphous. A successful measurement of T g depends on the ability of the polymer to form photophysical aggregates. The results obtained using this method for P3BT, PBTTT-C14, F8BT, and PDTSTPD are in agreement with values of T g that have been reported in the literature. Molecular dynamics simulations are used to show how the morphology evolves upon annealing: above the T g , an initially kinetically trapped morphology undergoes structural rearrangement to assume a more thermodynamically preferred structure. The temperature at which onset of this rearrangement occurs in the simulation is concomitant with the spectroscopically determined value of T g .

Agricultural development, extensive industrialization, and rapid growth of the global population have inadvertently been accompanied by environmental pollution. Water pollution is exacerbated by the decreasing ability of traditional treatment methods to comply with tightening environmental standards. This review provides a comprehensive description of the principles and applications of electrochemical methods for water purification, ion separations, and energy conversion. Electrochemical methods have attractive features such as compact size, chemical selectivity, broad applicability, and reduced generation of secondary waste. Perhaps the greatest advantage of electrochemical methods, however, is that they remove contaminants directly from the water, while other technologies extract the water from the contaminants, which enables efficient removal of trace pollutants. The review begins with an overview of conventional electrochemical methods, which drive chemical or physical transformations via Faradaic reactions at electrodes, and proceeds to a detailed examination of the two primary mechanisms by which contaminants are separated in nondestructive electrochemical processes, namely electrokinetics and electrosorption. In these sections, special attention is given to emerging methods, such as shock electrodialysis and Faradaic electrosorption. Given the importance of generating clean, renewable energy, which may sometimes be combined with water purification, the review also discusses inverse methods of electrochemical energy conversion based on reverse electrosorption, electrowetting, and electrokinetic phenomena. The review concludes with a discussion of technology comparisons, remaining challenges, and potential innovations for the field such as process intensification and technoeconomic optimization.

An extensive family of semi-random polymers was prepared via Stille polycondensation with varying contents of alkyl spacers incorporated into the polymer backbone to serve as a break in conjugation. This family was investigated to determine the effect of alkyl spacer length and percent incorporation on the optical, electronic, and mechanical properties. The optical bandgap was found to steadily increase from 1.53 to 1.70 eV as the amount of spacer was increased from 10 mol percent to 40 mol percent while the length of the spacer had little to no effect. In space charge limited current (SCLC) carrier mobility measurements, hole mobility was found to decrease as the amount of spacer increased but was found to steadily increase as the length of the spacer was increased from 6 to 10 carbons. Mechanical properties were observed by film-on-elastomer and film-on-water measurements, with low elastic moduli and high ductility attributed both to the break in conjugation as well as the semi-random structure of the polymer backbone. Measurements of the mechanical properties using the buckling method revealed elastic moduli between 0.14 and 1.3 GPa, and several polymers, when bonded to an elastomeric substrate, could be stretched beyond 80% strain. These polymers were further tested as free-standing films by obtaining a pull test on the surface of water, where we obtained tensile moduli between 0.13 and 0.75 GPa. These results indicate that semi-random polymers with conjugation-break spacers are promising candidates for further study in flexible electronics.

This paper describes the synthesis and characterization of a class of highly stretchable and degradable semiconducting polymers. These materials are multi-block copolymers (BCPs) in which the semiconducting blocks are based on the diketopyrrolopyrrole (DPP) unit flanked by furan rings and the insulating blocks are poly(ε-caprolactone) (PCL). The combination of stiff conjugated segments with flexible aliphatic polyesters produces materials that can be stretched >100%. Remarkably, BCPs containing up to 90 wt% of insulating PCL have the same field-effect mobility as the pure semiconductor. Spectroscopic (ultraviolet-visible absorption) and morphological (atomic force microscopic) evidence suggests that the semiconducting blocks form aggregated and percolated structures with increasing content of the insulating PCL. Both PDPP and PCL segments in the BCPs degrade under simulated physiological conditions. Such materials could find use in wearable, implantable, and disposable electronic devices.

This paper describes effects of the flexibility, length, and branching of side chains on the mechanical properties of low-bandgap semiconducting polymers. The backbones of the polymer chains comprise a diketopyrrolopyrrole (DPP) motif flanked by two furan rings and copolymerized by Stille polycondensation with thiophene (DPP2FT). The side chains of the DPP fall into three categories: linear alkyl (C8, C14, or C16), branched alkyl (ethylhexyl, EH, or hexyldecyl, HD), and linear oligo(ethylene oxide) (EO3, EO4, or EO5). Polymers bearing C8 and C14 side chains are obtained in low yields and thus not pursued. Thermal, mechanical, and electronic properties are plotted against the number of carbon and oxygen atoms in the side chain. We obtain consistent trends in the thermal and mechanical properties for branched alkyl and linear oligo(ethylene oxide) side chains. For example, the glass transition temperature (Tg) and elastic modulus decrease with increasing number of carbon and oxygen atoms, whereas the crack-onset strain increases. Among polymers with side chains of 16 carbon and oxygen atoms (C16, HD, and EO5), C16 exhibits the highest Tg and the greatest susceptibility to fracture. Hole mobility, as measured in thin-film transistors, appears to be a poor predictor of electronic performance for polymers blended with [60]PCBM in bulk heterojunction (BHJ) solar cells. For example, while EO3 and EO4 exhibit the lowest mobilities (< 10–2 cm2 V–1 s–1) in thin-film transistors, solar cells made using these materials performed the best (efficiency > 2.6%) in unoptimized devices. Conversely, C16 exhibits the highest mobility (≈ 0.2 cm2 V–1 s–1) but produces poor solar cells (efficiency < 0.01%). We attribute the lack of correlation between mobility and power conversion efficiency to unfavorable morphology in the BHJ solar cells. Given the desirable properties measured for EO3 and EO4, the use of flexible oligo(ethylene oxide) side chains is a successful strategy to impart mechanical deformability to organic solar cells, without sacrificing electronic performance.

One of the primary complications in characterizing the mechanical properties of thin films of semiconducting polymers for flexible electronics is the diverse range of fracture behavior that these materials exhibit. Although the mechanisms of fracture are well understood for brittle polymers, they are underexplored for ductile polymers. Experimentally, fracture can be characterized by observing the propagation of cracks and voids in an elongated film. For brittle polymers, we find that films bifurcate in such a way that the crack density increases linearly with applied strain (R 2 ≥ 0.91) at small strains. Linear regression is used to estimate the fracture strength and strain at fracture of each material using an existing methodology. For the case of ductile polymers, however, we find that diamond-shaped microvoids, which originate at pinholes and defects within the film, propagate with an aspect ratio that increases linearly with applied strain (R 2 ≥ 0.98). We define the rate of change of the aspect ratio of a microvoid with respect to applied strain as the “microvoid-propagation number.” This dimensionless film parameter, previously unreported, is a useful measure of ductility in thin films supported by an elastomer. To explore the significance of this parameter, we correlate the microvoid-propagation number with nominal ductility using several ductile polymer films of approximately equal thickness. Since the fracture of a film supported by a substrate depends on the elastic mismatch, we study the effect of this mismatch on the propagation of microvoids and observe that the microvoid-propagation number increases with increasing elastic mismatch. Moreover, we find that thicker films exhibit greater resistance to the propagation of fracture. We hypothesize that this behavior may be attributed to a larger volume of the plastic zone and a higher density of entanglements. To understand how the intrinsic mechanical properties of a film influence the fracture behavior on a substrate, we perform tensile tests of notched and unnotched films floated on the surface of water. We find a linear correlation (R 2 = 0.99) between the logarithm of the microvoid-propagation number and the fracture stress obtained from tensile tests of unnotched films.

The increasing popularity of nuclear energy necessitates development of new methods to treat water that becomes contaminated with radioactive substances. Because this polluted water comprises several dissolved species (not all of which are radioactive), selective accumulation of the radionuclides is desirable to minimize the volume of nuclear waste and to facilitate its containment or disposal. In this article, we use shock electrodialysis to selectively, continuously, and efficiently remove cobalt and cesium from a feed of dissolved lithium, cobalt, cesium, and boric acid. This formulation models the contaminated water commonly found in light-water reactors and in other nuclear processes. In a three-pass process, a consistent trade-off is observed between the recovery of decontaminated water and the percentage of cobalt removed, which offers flexibility in operating the system. For example, 99.5% of cobalt can be removed with a water recovery of 43%, but up to 66% of the water can be recovered if deionization of cobalt is allowed to drop to 98.3%. In general, the energy consumed during this process (ranging between 1.76 and 4.8 kW h m–3) is low because only charged species are targeted and virtually no energy is expended removing boric acid, the most abundant species in solution.

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