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    Thermoelectric Properties of N-Type Poly (Ether Ether Ketone)/Carbon Nanofiber Melt-Processed Composites
    (Basel : MDPI, 2022) Paleo, Antonio Jose; Krause, Beate; Soares, Delfim; Melle-Franco, Manuel; Muñoz, Enrique; Pötschke, Petra; Rocha, Ana Maria
    The thermoelectric properties, at temperatures from 30 °C to 100 °C, of melt-processed poly(ether ether ketone) (PEEK) composites prepared with 10 wt.% of carbon nanofibers (CNFs) are discussed in this work. At 30 °C, the PEEK/CNF composites show an electrical conductivity (σ) of ~27 S m−1 and a Seebeck coefficient (S) of −3.4 μV K−1, which means that their majority charge carriers are electrons. The origin of this negative Seebeck is deduced because of the impurities present in the as-received CNFs, which may cause sharply varying and localized states at approximately 0.086 eV above the Fermi energy level (EF) of CNFs. Moreover, the lower S, in absolute value, found in PEEK/CNF composites, when compared with the S of as-received CNFs (−5.3 μV K−1), is attributed to a slight electron withdrawing from the external layers of CNFs by the PEEK matrix. At temperatures from 30 °C to 100 °C, the σ (T) of PEEK/CNF composites, in contrast to the σ (T) of as-received CNFs, shows a negative temperature effect, understood through the 3D variable-range hopping (VRH) model, as a thermally activated hopping mechanism across a random network of potential wells. Moreover, their nonlinear S (T) follows the same behavior reported before for polypropylene composites melt-processed with similar CNFs at the same interval of temperatures.
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    Li+/H+ exchange of Li7La3Zr2O12 single and polycrystals investigated by quantitative LIBS depth profiling
    (Cambridge : Royal Society of Chemistry, 2022) Smetaczek, Stefan; Limbeck, Andreas; Zeller, Veronika; Ring, Joseph; Ganschow, Steffen; Rettenwander, Daniel; Fleig, Jürgen
    Li7La3Zr2O12 (LLZO) garnets are highly attractive to be used as solid electrolyte in solid-state Li batteries. However, LLZO suffers from chemical interaction with air and humidity, causing Li+/H+ exchange with detrimental implication on its performance, processing and scalability. To better understand the kinetics of the detrimental Li+/H+ exchange and its dependence on microstructural features, accelerated Li+/H+ exchange experiments were performed on single crystalline and polycrystalline LLZO, exposed for 80 minutes to 80 °C hot water. The resulting chemical changes were quantified by analytical methods, i.e. inductively coupled plasma optical emission spectroscopy (ICP-OES) and laser induced breakdown spectroscopy (LIBS). From the time dependence of the Li+ enrichment in the water, measured by ICP-OES, a bulk interdiffusion coefficient of Li+/H+ could be determined (7 × 10−17 m2 s−1 at 80 °C). Depth dependent concentrations were obtained from the LIBS data for both ions after establishing a calibration method enabling not only Li+ but also H+ quantification in the solid electrolyte. Short interdiffusion lengths in the 1 μm range are found for the single crystalline Ga:LLZO, in accordance with the measured bulk diffusion coefficient. In polycrystalline Ta:LLZO, however, very long diffusion tails in the 20 μm range and ion exchange fractions up to about 70% are observed. Those are attributed to fast ion interdiffusion along grain boundaries. The severe compositional changes also strongly affect the electrical properties measured by impedance spectroscopy. This study highlights that microstructural effects may be decisive for the Li+/H+ ion exchange kinetics of LLZO.
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    Different Radial Modification Profiles Observed on APPJ-Treated Polypropylene Surfaces according to the Distance between Plasma Outlet and Target
    (Basel : MDPI, 2022) do Nascimento, Fellype; Silva Leal, Bruno; Quade, Antje; Kostov, Konstantin Georgiev
    The plasma jet transfer technique relies on a conductive wire at floating potential, which, upon entering in contact with a primary discharge, is capable of igniting a small plasma plume at the distal end of a long flexible plastic tube. In this work, two different long tube configurations were employed for the surface modification of polypropylene (PP) samples using argon as the working gas. One of the jet configurations has a thin copper (Cu) wire, which was installed inside the long tube. In the other configuration, the floating electrode is a metallic mesh placed between two plastic tubes in a coaxial arrangement. In the first case, the tip of the Cu wire is in direct contact with the working gas at the plasma outlet, whereas, in the second, the inner plastic tube provides an additional dielectric barrier that prevents the conductor from being in contact with the gas. Water contact angle (WCA) measurements on treated PP samples revealed that different surface modification radial profiles are formed when the distance (d) between the plasma outlet and target is changed. Moreover, it was found that the highest WCA reduction does not always occur at the point where the plasma impinges the surface of the material, especially when the d value is small. Through X-ray photoelectron spectroscopy (XPS) analysis, it was confirmed that the WCA values are directly linked to the oxygen-functional groups formed on the PP surfaces after the plasma treatment. An analysis of the WCA measurements along the surface, as well as their temporal evolution, together with the XPS data, suggest that, when the treatment is performed at small d values, the plasma jet removes some functional groups at the point where the plasma hits the surface, thus leading to peculiar WCA profiles.
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    Optical, electrical and chemical properties of PEO:I2 complex composite films
    (Heidelberg [u.a.] : Springer, 2022) Telfah, Ahmad; Al-Bataineh, Qais M.; Tolstik, Elen; Ahmad, Ahmad A.; Alsaad, Ahmad M.; Ababneh, Riad; Tavares, Carlos J.; Hergenröder, Roland
    Synthesized PEO:I2 complex composite films with different I2 concentrations were deposited onto fused silica substrates using a dip-coating method. Incorporation of PEO films with I2 increases the electrical conductivity of the composite, reaching a maximum of 46 mS/cm for 7 wt% I2. The optical and optoelectronic properties of the complex composite films were studied using the transmittance and reflectance spectra in the UV-Vis region. The transmittance of PEO decreases with increasing I2 content. From this study, the optical bandgap energy decreases from 4.42 to 3.28 eV as I2 content increases from 0 to 7 wt%. In addition, the refractive index for PEO films are in the range of 1.66 and 2.00.1H NMR spectra of pure PEO film shows two major peaks at 3.224 ppm and 1.038 ppm, with different widths assigned to the mobile polymer chains in the amorphous phase, whereas the broad component is assigned to the more rigid molecules in the crystalline phase, respectively. By adding I2 to the PEO, both peaks (amorphous and crystal) are shifted to lower NMR frequencies indicating that I2 is acting as a Lewis acid, and PEO is acting as Lewis base. Hence, molecular iodine reacts favorably with PEO molecules through a charge transfer mechanism, and the formation of triiodide (I3-), the iodite (IO2-) anion, I 2· · · PEO and I2+···PEO complexes. PEO:I2 complex composite films are expected to be suitable for optical, electrical, and optoelectronic applications.
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    Inactivation of airborne bacteria by plasma treatment and ionic wind for indoor air cleaning
    (Hoboken, NJ : Wiley Interscience, 2020) Prehn, Franziska; Timmermann, Eric; Kettlitz, Manfred; Schaufler, Katharina; Günther, Sebastian; Hahn, Veronika
    Airborne bacteria are a general problem in medical or health care facilities with a high risk for nosocomial infections. Rooms with a continuous airflow, such as operation theaters, are of particular importance due to a possible dissemination and circulation of pathogens including multidrug-resistant microorganisms. In this regard, a cold atmospheric-pressure plasma (CAP) may be a possibility to support usual disinfection procedures due to its decontaminating properties. The aim of this study was to determine the antimicrobial efficacy of a plasma decontamination module that included a dielectric barrier discharge for plasma generation. Experimental parameters such as an airflow velocity of 4.5 m/s and microbial contaminations of approximately 6,000 colony-forming units (cfu)/m3 were used to simulate practical conditions of a ventilation system in an operating theater. The apathogenic microorganism Escherichia coli K12 DSM 11250/NCTC 10538 and the multidrug-resistant strains E. coli 21181 and 21182 (isolated from patients) were tested to determine the antimicrobial efficacy. In summary, the number of cfu was reduced by 31–89% for the tested E. coli strains, whereby E. coli K12 was the most susceptible strain toward inactivation by the designed plasma module. A possible correlation between the number or kind of resistances and susceptibility against plasma was discussed. The inactivation of microorganisms was affected by plasma intensity and size of the plasma treatment area. In addition, the differences of the antimicrobial efficacies caused through the nebulization of microorganisms in front (upstream) or behind (downstream) the plasma source were compared. The presence of ionic wind had no influence on the reduction of the number of cfu for E. coli K12, as the airflow velocity was too high for a successful precipitation, which would be a prerequisite for an increased antimicrobial efficacy. The inactivation of the tested microorganisms confirms the potential of CAP for the improvement of air quality. The scale-up of this model system may provide a novel tool for an effective air cleaning process.
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    A block copolymer templated approach for the preparation of nanoporous polymer structures and cellulose fiber hybrids by ozone treatment
    (Cambridge : RSC Publ., 2022) Gemmer, Lea; Hu, Qiwei; Niebuur, Bart-Jan; Kraus, Tobias; Balzer, Bizan N.; Gallei, Markus
    Functional amphiphilic block copolymers (BCPs) are versatile, smart, and promising materials that are often used as soft templates in nanoscience. BCPs generally feature the capability of microphase-separation leading to various interesting morphologies at the nanometer length scale. Materials derived from BCPs can be converted into porous structures while retaining the underlying morphology of the matrix material. Here, a convenient and scalable approach for the fabrication of porous functional polyvinylpyridines (P2VP) is introduced. The BCP polyisoprene-block-P2VP (PI-b-P2VP) is obtained via sequential anionic polymerization of the respective monomers and used to form either BCP films in the bulk state or a soft template in a composite with cellulose fibers. Cross-linking of the BCPs with 1,4-diiodobutane is conducted and subsequently PI domains are selectively degraded inside the materials using ozone, while preserving the porous and tailor-made P2VP nanostructure. Insights into the feasibility of the herein presented strategy is supported by various polymer characterization methods comprising nuclear magnetic resonance (NMR), size exclusion chromatography (SEC), and differential scanning calorimetry (DSC). The resulting bulk- and composite materials are investigated regarding their morphology and pore formation by scanning electron microscopy (SEM), atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS). Furthermore, chemical conversions were examined by energy dispersive X-ray spectroscopy (EDS), attenuated total reflection Fourier-transformation infrared spectroscopy (ATR-FTIR) and water contact angle (WCA) measurements. By this convenient strategy the fabrication of functional porous P2VP in the bulk state and also within sustainable cellulose composite materials is shown, paving the synthetic strategy for the generation of a new family of stimuli-responsive sustainable materials.
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    Studies on Stress Corrosion Cracking of Vit 105 Bulk Metallic Glass
    (Lausanne : Frontiers Media S.A., 2020) Gebert, A.; Geissler, D.; Pilz, S.; Uhlemann, M.; Davani, F.A.; Hilke, S.; Rösner, H.; Wilde, G.
    The project “Stress Corrosion Cracking of Zr-based Bulk Metallic Glasses” (SCC of Zr-BMGs) within PP1594 mainly dealt with mechanical–corrosive interactions and failure of this class of metastable materials. It focused on one of the most application-relevant zirconium (Zr)-BMG, Vit(reloy) 105, with composition Zr52.5Cu17.9Ni14.6Al10Ti5 (at.%). Even though this BMG is known as an extraordinary glass former, the metallurgical processing is still a critical issue. In contrast to conventional processing, i.e., arc melting of master alloy ingots from single constituents, a different route using binary pre-alloys for the master alloys production was applied and led to superior mechanical properties upon mechanical testing under tensile and three-point-bending (3PB) conditions in air. As a reference and for a detailed understanding of failure, fracture, and cracking of Zr-based BMG in air, notched specimen 3PB experiments with in situ microscopic observation were done and the still controversial interpretation of the mechanical behavior of BMG in the framework of fracture mechanics was addressed. The specimen from the in situ 3PB tests served for transmission electron microscopy (TEM) investigations on the structural nature of shear bands in BMG on the atomistic scale. Altogether, complete crack paths could be observed and analyzed, and based on this, details of the shear band-driven crack growth are described. While in first SCC studies using a newly developed setup full cross section (3PB) bars were investigated, in recent in situ experiments, notched specimens were tested in 0.01 M NaCl, yielding strong evidence for a catastrophic failure due to hydrogen embrittlement (HE). The known susceptibility to pitting corrosion in halide-containing environments is only the initial stage for failure under SCC conditions. Once pitting is initiated, the local electrode potential is severely reduced. Further, the hydrolysis reaction of oxidized Zr4+ to zirconyl ions ZrO2+ during local BMG dissolution produces H+ and, thus, a local acidic environment that enables proton reduction and hydrogen absorption in the stressed BMG region. The peculiar failure and fracture surface characteristics as well as the proven local reduction of the pH value in the vicinity of the notch during in situ experiments clearly account for the proposed HE-SCC failure mechanism.
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    Flexible and transparent electrodes imprinted from Au nanowires: stability and ageing
    (Cambridge : Royal Society of Chemistry, 2022) Engel, Lukas F.; González-García, Lola; Kraus, Tobias
    We study the stability of flexible transparent electrodes (FTEs) that were self-assembled from ultra-thin gold nanowires (AuNW) by direct nanoimprinting of inks with different particle concentrations (1 to 10 mg mL−1). The resulting lines were less than 3 μm wide and contained bundles of AuNW with oleylamine (OAm) ligand shells. Small-angle X-ray scattering confirmed a concentration-independent bundle structure. Plasma sintering converted the wire assemblies into lines with a thin metal shell that contributes most to electrical conductivity and covers a hybrid core. We studied the relative change in sheet resistance and the morphology of the FTEs with time. The sheet resistance increased at all concentrations, but at different rates. The metal shell aged by de-wetting and pore formation. The hybrid core de-mixed and densified, which led to a partial collapse of the shell. Residual organics migrated through the shell via its pores. Lines formed at low concentration (cAu = 2 to 3 mg mL−1) contained less residual organics and aged slower than those formed at high cAu ≥ 5 mg mL−1. We passivated the conductive shell with thin, adsorbed layers of PEDOT:PSS and found that it decelerated degradation by slowing surface diffusion and hindering further rupture of the shell. Thick capping layers prevented degradation entirely and stopped pore formation.
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    Reduction of biofouling of a microfiltration membrane using amide functionalities-Hydrophilization without changes in morphology
    (Basel : MDPI, 2020) Breite, Daniel; Went, Marco; Prager, Andrea; Kühnert, Mathias; Schulze, Agnes
    A major goal of membrane science is the improvement of the membrane performance and the reduction of fouling effects, which occur during most aqueous filtration applications. Increasing the surface hydrophilicity can improve the membrane performance (in case of aqueous media) and decelerates membrane fouling. In this study, a PES microfiltration membrane (14,600 L m−2 h−1 bar−1) was hydrophilized using a hydrophilic surface coating based on amide functionalities, converting the hydrophobic membrane surface (water contact angle, WCA: ~90°) into an extremely hydrophilic one (WCA: ~30°). The amide layer was created by first immobilizing piperazine to the membrane surface via electron beam irradiation. Subsequently, a reaction with 1,3,5-benzenetricarbonyl trichloride (TMC) was applied to generate an amide structure. The presented approach resulted in a hydrophilic membrane surface, while maintaining permeance of the membrane without pore blocking. All membranes were investigated regarding their permeance, porosity, average pore size, morphology (SEM), chemical composition (XPS), and wettability. Soxhlet extraction was carried out to demonstrate the stability of the applied coating. The improvement of the modified membranes was demonstrated using dead-end filtration of algae solutions. After three fouling cycles, about 60% of the initial permeance remain for the modified membranes, while only ~25% remain for the reference.
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    A Theoretical and Experimental Analysis of the Effect of Nanoclay on Gas Perm-Selectivity of Biodegradable PLA/EVA Blends in the Presence and Absence of Compatibilizer
    (New York, NY [u.a.] : Wiley InterScience, 2020) Karimpour-Motlagh, Navid; Moghadam, Abolfazl Salehi; Khonakdar, Hossein Ali; Jafari, Seyed Hassan; Wagenknecht, Udo; Kasbi, Sina Farahani; Shojaei, Shahrokh; Mirzaee, Ramin
    Poly (lactic acid) (PLA)-based compounds are widely used in thin-film and food packaging industries. Herein, PLA/ethylene vinyl acetate copolymer (EVA)/nanoclay nanocomposites are prepared in various compositions by melt blending. The gas permeability against N2, CO2, and O2 gases is determined as a function of composition and morphology of the nanocomposites. Inclusion of high aspect ratio of platelet-like nanoclay to the blend reduces the gas diffusion. The best barrier properties against all gases is observed on introducing 5 wt% poly(ethylene/n-butyl acrylate glycidyl methacrylate) copolymer as compatibilizer to the PLA/EVA/nanoclay (75/25/5) system. The scanning and transmission electron microscopic analyses and wide-angle X-ray scattering studies reveal that inclusion of compatibilizer to the filled-blends improves the blend morphology, dispersion state, and intercalation level of clay platelets which are preferably localized at the interface of the blend. Analysis of selectivity parameter (a) shows the lowest O2 permeability and the highest aCO2/N2 and aO2/N2 values for the compatibilized filled-blend (75/25/5/5). In situ aspect ratio of clay and the degree of intercalation are theoretically evaluated based on the permeability data using various empirical models. It is found that the compatibilized filled-blend has the highest aspect ratio and intercalation level that are responsible for the optimum perm-selectivity performance. © 2020 The Authors. Published by Wiley-VCH GmbH