Selective and Chemical-Free Removal of Toxic Heavy Metal Cations from Water Using Shock Ion Extraction.

Electrochemical methods are known to have attractive features and capabilities when used for ion separations and water purification. In this study, we developed a new process called shock ion extraction (shock IX) for selective and chemical-free removal of toxic heavy metals from water. Shock IX is a hybrid process that combines shock electrodialysis (shock ED) and ion exchange using an ion exchange resin wafer (IERW), and this method can be thought of functionally as an electrochemically assisted variation of traditional ion exchange. In particular, shock IX exhibits greater ion removal and selectivity for longer periods of time, compared to the use of ion exchange alone. The use of an IERW in shock ED also increases multivalent ion selectivity, reduces energy consumption, and improves the hydrodynamics and scalability of the system.

Electrochemical Methods for Water Purification, Ion Separations, and Energy Conversion.

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.

Theory of shock electrodialysis I: Water dissociation and electrosmotic vortices.

Shock electrodialysis (shock ED), an emerging electrokinetic process for water purification, leverages the new physics of deionization shock waves in porous media. In previous work, a simple leaky membrane model with surface conduction can explain the propagation of deionization shocks in a shock ED system, but it cannot quantitatively predict the deionization and conductance (which determines the energy consumption), and it cannot explain the selective removal of ions in experiments. This two-part series of work establishes a more comprehensive model for shock ED, which applies to multicomponent electrolytes and any electrical double layer thickness, captures the phenomena of electroosmosis, diffusioosmosis, and water dissociation, and incorporates more realistic boundary conditions. In this paper, we will present the model details and show that hydronium transport and electroosmotic vortices (at the inlet and outlet) play important roles in determining the deionization and conductance in shock ED. We also find that the results are quantitatively consistent with experimental data in the literature. Finally, the model is used to investigate design strategies for scale up and optimization.

Theory of shock electrodialysis II: Mechanisms of selective ion removal.

Shock electrodialysis (shock ED), an emerging nonlinear electrokinetic process for water treatment, has recently showed its capability to selectively remove multivalent cations from electrolyte mixtures. However, the mechanisms have not been understood yet. Based on the depth-averaged model developed in the first-part of the series paper for planer shock ED system, this work focuses on the mechanisms of selective ion removal. We first assume plug feed flow and do scaling analysis, and identify three possible mechanisms of selective removal of multivalent cations: smaller concentration left behind deionization zone, affinity to the charged surface where non-slip boundary slows down the velocity, and stronger push-back by streaming potential. Then we use numerical simulations to prove our hypothesis and show additional contribution from electroosmotic flow. Simulation results show that Mg is more removed from Na-Mg-Cl mixture at overlimiting current, which is qualitatively consistent with experiment results in literature.

Novel ionic separation mechanisms in electrically driven membrane processes.

Electromembrane processes including electrodialysis (ED) and related processes are usually limited by diffusion transport of ions from a bulk solution to ion exchange membranes. The diffusion limited current (DLC) occurs when the concentration at membrane surfaces vanishes and approaches zero. Increasing the applied potential difference above this point has no substantial effect on ion transport and causes operational problems such as low current efficiency, high energy consumption, and mineral scaling. However, it is evident from numerous studies that operating at overlimiting current (OLC) is possible and allows one to enhance the mass transfer of an electromembrane process. While OLC is sometimes possible by electrochemical means, such as water splitting or current induced membrane discharge, it has been found that exotic ion transport mechanisms, such as ion concentration polarization in micro/nanofluidic system, deionization shock waves, and ionic bridges, can provide novel electrokinetic means of achieving OLC. In this paper, these novel ionic separation mechanisms and their role in enhanced current transfer are reviewed in the context of emerging electromembrane processes, such as shock ED and electrodeionization (EDI).

Continuous Separation of Radionuclides from Contaminated Water by Shock Electrodialysis.

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.

Healable Thermoplastic for Kinesthetic Feedback in Wearable Haptic Devices.

The word "haptics" refers to technologies designed to stimulate the tactile and kinesthetic senses. Kinesthesia-the sense of motion-is triggered by imposing forces upon the joints, tendons, and muscles to recreate the geometry and stiffness of objects, as may be useful in physical therapy or virtual reality. Here, we introduce a form of kinesthetic feedback by manipulating the mechanical properties of spandex impregnated with a thermoplastic polymer. Heating or cooling this textile-thermoplastic composite just above or below its glass transition temperature (T g) dramatically changes its mechanical properties (corresponding to a decrease in storage modulus from 36 MPa to 0.55 MPa). In the form of a glove, the composite can also be healed after inadvertent overextension in its stiffened state by heating it above its T g. When fitted with thermoelectric devices for active heating and cooling, the flexible or stiffened state of a glove can be perceived by human subjects. As an example of a human-machine interface, the glove is used to control a robotic finger. When the robotic finger makes contact with a wall, a signal is sent to thermoelectric devices in the glove to cool (stiffen the finger) and thus provide kinesthetic feedback to the user.

Influence of Systematic Incorporation of Conjugation-Break Spacers into Semi-Random Polymers on Mechanical and Electronic Properties.

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.

Measurement of Cohesion and Adhesion of Semiconducting Polymers by Scratch Testing: Effect of Side-Chain Length and Degree of Polymerization.

Most advantages of organic electronic materials are enabled by mechanical deformability, as flexible (and stretchable) devices made from these materials must be able to withstand roll-to-roll printing and survive mechanical insults from the external environment. Cohesion and adhesion are two properties that dictate the mechanical reliability of a flexible organic electronic device. In this paper, progressive-load scratch tests are used for the first time to correlate the cohesive and adhesive behavior of poly(3-alkylthiophenes) (P3ATs) with respect to two molecular parameters: length of the alkyl side chain and molecular weight. In contrast to metrological techniques based on buckling or pull testing of pseudofreestanding films, scratch tests reveal information about both the cohesive and adhesive properties of thin polymeric films from a single procedure. Our data show a decrease in cohesion and adhesion, that is, a decrease in overall mechanical robustness, with increasing length of the side chain. This behavior is likely due to increases in free volume and concomitant decreases in the glass transition temperature. In contrast, we observe increases in both the cohesion and adhesion with increasing molecular weight. This behavior is attributed to an increased density of entanglements with high molecular weight, which manifests as increased extensibility. These observations are consistent with the results of molecular dynamics simulations. Interestingly, the normal (applied) forces associated with cohesive and adhesive failure are directly proportional to the average degree of polymerization, as opposed to simply the molecular weight, as the length of the alkyl side chain increases the molecular weight without increasing the degree of polymerization.

Effects of flexibility and branching of side chains on the mechanical properties of low-bandgap conjugated polymers.

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 (T g) 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 T g 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.

Stretchable and Degradable Semiconducting Block Copolymers.

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.