Tailoring Membrane Surface Charges: A Novel Study on Electrostatic Interactions during Membrane Fouling

In this work we aim to show that the overall surface potential is a key factor to understand and predict anti-fouling characteristics of a polymer membrane. Therefore, polyvinylidene fluoride membranes were modified by electron beam-induced grafting reactions forming neutral, acidic, alkaline or zwitterionic structures on the membrane surface. The differently charged membranes were investigated regarding their surface properties using diverse analytical methods: zeta potential, static and dynamic water contact angle, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Porosimetry measurements proved that there is no pore blocking due to the modifications. Monodisperse suspensions of differently charged polystyrene beads were synthesized by a radical emulsion polymerization reaction and were used as a model fouling reagent, preventing comparability problems known from current literature. To simulate membrane fouling, different bead suspensions were filtered through the membranes. The fouling characteristics were investigated regarding permeation flux decline and concentration of model fouling reagent in filtrate as well as by SEM. By considering electrostatic interactions equal to hydrophobic interactions we developed a novel fouling test system, which enables the prediction of a membrane’s fouling tendency. Electrostatic forces are dominating, especially when charged fouling reagents are present, and can help to explain fouling characteristics that cannot be explained considering the surface wettability

Biocatalytic Self-Cleaning Polymer Membranes

Polymer membrane surfaces have been equipped with the digestive enzyme trypsin. Enzyme immobilization was performed by electron beam irradiation in aqueous media within a one-step method. Using this method, trypsin was covalently and side-unspecific attached to the membrane surface. Thus, the use of preceding polymer functionalization and the use of toxic solvents or reagents can be avoided. The resulting membranes showed significantly improved antifouling properties as demonstrated by repeated filtration of protein solutions. Furthermore, the biocatalytic membrane can be simply “switched on” to actively degrade a fouling layer on the membrane surface and regain the initial permeability. The membrane pore structure (pore size and porosity) was neither damaged by the electron beam treatment nor blocked by the enzyme loading, ensuring a stable membrane performance

Functionalized and Platinum-Decorated Multi-Layer Oxidized Graphene as a Proton, and Electron Conducting Separator in Solid Acid Fuel Cells

In the present article, electrodes containing a composite of platinum on top of a plasma-oxidized multi-layer graphene film are investigated as model electrodes that combine an exceptional high platinum utilization with high electrode stability. Graphene is thereby acting as a separator between the phosphate-based electrolyte and the platinum catalyst. Electrochemical impedance measurements in humidified hydrogen at 240 °C show area-normalized electrode resistance of 0.06 Ω·cm−2 for a platinum loading of ∼60 µgPt·cm−2, resulting in an outstanding mass normalized activity of almost 280 S·mgPt−1, exceeding even state-of-the-art electrodes. The presented platinum decorated graphene electrodes enable stable operation over 60 h with a non-optimized degradation rate of 0.15% h−1, whereas electrodes with a similar design but without the graphene as separator are prone to a very fast degradation. The presented results propose an efficient way to stabilize solid acid fuel cell electrodes and provide valuable insights about the degradation processes which are essential for further electrode optimization

Phase and grain size engineering in Ge-Sb-Te-O by alloying with La-Sr-Mn-O towards improved material properties

Ge-Sb-Te alloys are promising materials for non-volatile memory applications. Alloying of the materials with various elements is considered as prospective approach to enhance material properties. This work reports on the preparation and characterization of pure Ge-Sb-Te-O (GSTO) and alloyed with La-Sr-Mn-O (LSMO) thin films. Thermal heating of amorphous thin films to different temperatures show distinct crystallization behavior. A general trend is the decrease in the size of GSTO crystallites and the suppression in the formation of stable trigonal GSTO phase with increasing content of LSMO. Microstructural studies by transmission electron microscopy show the formation of metastable GSTO nanocrystallites dispersed in the amorphous matrix. Analysis of local chemical bonding by X-ray spectroscopy reveal the presence of different oxides in the GSTO-LSMO composites. Moreover, the composites with a high LSMO content exhibit higher crystallization temperature and significant larger sheet resistance in amorphous and crystalline phase, while a memory device made of GSTO-LSMO alloy reveals bipolar switching and synaptic behavior. In addition, the amount of LSMO in GSTO-LSMO thin films influences their optical properties and band gap. Overall, the results of this work reveal the highly promising potential of GSTO-LSMO nanocomposites for data storage and reconfigurable photonic applications as well as neuro-inspired computing

Low-temperature atmospheric pressure plasma conversion of polydimethylsiloxane and polysilazane precursor layers to oxide thin films

We study the conversion of two polymeric silicon precursor compound layers (perhydropolysilazane and polydimethylsiloxane) on a silicon wafer and polyethylene terephthalate substrates to silicon oxide thin films using a pulsed atmospheric pressure plasma jet. Varying the scan velocity and the number of treatments results in various film compositions, as determined by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The mechanism suggested for the conversion process includes the decomposition of the precursor triggered by plasma-produced species, the oxidation of the surface, and finally, the diffusion of oxygen into the film, while gases produced during the precursor decomposition diffuse out of the film. The latter process is possibly facilitated by local plasma heating of the surface. The precursor conversion appears to depend sensitively on the balance between the different contributions to the conversion mechanism

The immersion freezing behavior of ash particles from wood and brown coal burning

It is generally known that ash particles from coal combustion can trigger ice nucleation when they interact with water vapor and/or supercooled droplets. However, data on the ice nucleation of ash particles from different sources, including both anthropogenic and natural combustion processes, are still scarce. As fossil energy sources still fuel the largest proportion of electric power production worldwide, and biomass burning contributes significantly to the global aerosol loading, further data are needed to better assess the ice nucleating efficiency of ash particles. In the framework of this study, we found that ash particles from brown coal (i.e., lignite) burning are up to 2 orders of magnitude more ice active in the immersion mode below −32 °C than those from wood burning. Fly ash from a coal-fired power plant was shown to be the most efficient at nucleating ice. Furthermore, the influence of various particle generation methods on the freezing behavior was studied. For instance, particles were generated either by dispersion of dry sample material, or by atomization of ash–water suspensions, and then led into the Leipzig Aerosol Cloud Interaction Simulator (LACIS) where the immersion freezing behavior was examined. Whereas the immersion freezing behavior of ashes from wood burning was not affected by the particle generation method, it depended on the type of particle generation for ash from brown coal. It was also found that the common practice of treating prepared suspensions in an ultrasonic bath to avoid aggregation of particles led to an enhanced ice nucleation activity. The findings of this study suggest (a) that ash from brown coal burning may influence immersion freezing in clouds close to the source and (b) that the freezing behavior of ash particles may be altered by a change in sample preparation and/or particle generation

Synthesis of High Crystalline TiO2 Nanoparticles on a Polymer Membrane to Degrade Pollutants from Water

Titanium dioxide (TiO2) is described as an established material to remove pollutants from water. However, TiO2 is still not applied on a large scale due to issues concerning, for example, the form of use or low photocatalytic activity. We present an easily upscalable method to synthesize high active TiO2 nanoparticles on a polyethersulfone microfiltration membrane to remove pollutants in a continuous way. For this purpose, titanium(IV) isopropoxide was mixed with water and hydrochloric acid and treated up to 210 °C. After cooling, the membrane was simply dip-coated into the TiO2 nanoparticle dispersion. Standard characterization was undertaken (i.e., X-ray powder diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, water permeance, contact angle). Degradation of carbamazepine and methylene blue was executed. By increasing synthesis temperature crystallinity and photocatalytic activity elevates. Both ultrasound modification of nanoparticles and membrane pre-modification with carboxyl groups led to fine distribution of nanoparticles. The ultrasound-treated nanoparticles gave the highest photocatalytic activity in degrading carbamazepine and showed no decrease in degradation after nine times of repetition. The TiO2 nanoparticles were strongly bound to the membrane. Photocatalytic TiO2 nanoparticles with high activity were synthesized. The innovative method enables a fast and easy nanoparticle production, which could enable the use in large-scale water cleaning

Radiation-Induced Graft Immobilization (RIGI): Covalent Binding of Non-Vinyl Compounds on Polymer Membranes

Radiation-induced graft immobilization (RIGI) is a novel method for the covalent binding of substances on polymeric materials without the use of additional chemicals. In contrast to the well-known radiation-induced graft polymerization (RIGP), RIGI can use non-vinyl compounds such as small and large functional molecules, hydrophilic polymers, or even enzymes. In a one-step electron-beam-based process, immobilization can be performed in a clean, fast, and continuous operation mode, as required for industrial applications. This study proposes a reaction mechanism using polyvinylidene fluoride (PVDF) and two small model molecules, glycine and taurine, in aqueous solution. Covalent coupling of single molecules is achieved by radical recombination and alkene addition reactions, with water radiolysis playing a crucial role in the formation of reactive solute species. Hydroxyl radicals contribute mainly to the immobilization, while solvated electrons and hydrogen radicals play a minor role. Release of fluoride is mainly induced by direct ionization of the polymer and supported by water. Hydrophobic chains attached to cations appear to enhance the covalent attachment of solutes to the polymer surface. Computational work is complemented by experimental studies, including X-ray photoelectron spectroscopy (XPS) and fluoride high-performance ion chromatography (HPIC)

Role of Reaction Intermediate Diffusion on the Performance of Platinum Electrodes in Solid Acid Fuel Cells

Understanding the reaction pathways for the hydrogen oxidation reaction (HOR) and the oxygen reduction reaction (ORR) is the key to design electrodes for solid acid fuel cells (SAFCs). In general, electrochemical reactions of a fuel cell are considered to occur at the triple-phase boundary where an electrocatalyst, electrolyte and gas phase are in contact. In this concept, diffusion processes of reaction intermediates from the catalyst to the electrolyte remain unconsidered. Here, we unravel the reaction pathways for open-structured Pt electrodes with various electrode thicknesses from 15 to 240 nm. These electrodes are characterized by a triple-phase boundary length and a thickness-depending double-phase boundary area. We reveal that the double-phase boundary is the active catalytic interface for the HOR. For Pt layers ≤ 60 nm, the HOR rate is rate-limited by the processes at the gas/catalyst and/or the catalyst/electrolyte interface while the hydrogen surface diffusion step is fast. For thicker layers (>60 nm), the diffusion of reaction intermediates on the surface of Pt be-comes the limiting process. For the ORR, the predominant reaction pathway is via the triple-phase boundary. The double-phase boundary contributes additionally with a diffusion length of a few nanometers. Based on our results, we propose that the molecular reaction mechanism at the electrode interfaces based upon the triple-phase boundary concept may need to be extended to an effective area near the triple-phase boundary length to include all catalytically relevant diffusion processes of the reaction intermediates. © 2021 by the authors. Licensee MDPI, Basel, Switzerland