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- ItemThermoelectric 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 MariaThe 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.
- ItemA 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, RaminPoly (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
- ItemEnhanced growth of lapine anterior cruciate ligament-derived fibroblasts on scaffolds embroidered from poly(L-lactide-co-ε-caprolactone) and polylactic acid threads functionalized by fluorination and hexamethylene diisocyanate cross-linked collagen foams(Basel : Molecular Diversity Preservation International, 2020) Gögele, Clemens; Hahn, Judith; Elschner, Cindy; Breier, Annette; Schröpfer, Michaela; Prade, Ina; Meyer, Michael; Schulze-Tanzil, GundulaReconstruction of ruptured anterior cruciate ligaments (ACLs) is limited by the availability and donor site morbidity of autografts. Hence, a tissue engineered graft could present an alternative in the future. This study was undertaken to determine the performance of lapine (L) ACL-derived fibroblasts on embroidered poly(l-lactide-co-e-caprolactone) (P(LA-CL)) and polylactic acid (PLA) scaffolds in regard to a tissue engineering approach for ACL reconstruction. Surface modifications of P(LA-CL)/PLA by gas-phase fluorination and cross-linking of a collagen foam using either ethylcarbodiimide (EDC) or hexamethylene diisocyanate (HMDI) were tested regarding their influence on cell adhesion, growth and gene expression. The experiments were performed using embroidered P(LA-CL)/PLA scaffolds that were seeded dynamically or statically with LACL-derived fibroblasts. Scaffold cytocompatibility, cell survival, numbers, metabolic activity, ultrastructure and sulfated glycosaminoglycan (sGAG) synthesis were evaluated. Quantitative real-time polymerase chain reaction (QPCR) revealed gene expression of collagen type I (COL1A1), decorin (DCN), tenascin C (TNC), Mohawk (MKX) and tenomodulin (TNMD). All tested scaffolds were highly cytocompatible. A significantly higher cellularity and larger scaffold surface areas colonized by cells were detected in HMDI cross-linked and fluorinated scaffolds compared to those cross-linked with EDC or without any functionalization. By contrast, sGAG synthesis was higher in controls. Despite the fact that the significance level was not reached, gene expressions of ligament extracellular matrix components and differentiation markers were generally higher in fluorinated scaffolds with cross-linked collagen foams. LACL-derived fibroblasts maintained their differentiated phenotype on fluorinated scaffolds supplemented with a HMDI cross-linked collagen foam, making them a promising tool for ACL tissue engineering. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.
- ItemCharacterisation and Modelling of Moisture Gradients in Polyamide 6(Basel : MDPI, 2021) Sambale, Anna Katharina; Maisl, Michael; Herrmann, Hans-Georg; Stommel, MarkusPolyamide 6 (PA6) is able to absorb water from the surrounding air and bond to it by forming hydrogen bonds between the carbonamide groups of its molecular chains. Diffusion processes cause locally different water concentrations in the (component) cross-section during the sorption process, resulting in locally different mechanical properties due to the water-induced plasticisation effect. However, the water content of PA6 is usually specified as an integral value, so no information about a local water distribution within a component is provided. This paper shows a method to characterise moisture distributions within PA6 samples using low-energy computer tomography (CT) techniques and comparing the reconstructed results with a developed finite elements (FE) modelling method based on Fick’s diffusion laws with concentration-dependent diffusion coefficients. For this purpose, the ageing of the samples at two different water bath temperatures as well as at different integral water contents are considered. The results obtained by CT reconstruction and FE modelling are in very good agreement, so that the concentration distributions by water sorption of PA6 calculated by FEM can be regarded as validated.
- ItemDeepening the insight into poly(butylene oxide)-block-poly(glycidol) synthesis and self-assemblies: micelles, worms and vesicles(Cambridge : RSC, 2020) Wehr, Riccardo; Gaitzsch, Jens; Daubian, Davy; Fodor, Csaba; Meier, WolfgangAqueous self-assembly of amphiphilic block copolymers is studied extensively for biomedical applications like drug delivery and nanoreactors. The commonly used hydrophilic block poly(ethylene oxide) (PEO), however, suffers from several drawbacks. As a potent alternative, poly(glycidol) (PG) has gained increasing interest, benefiting from its easy synthesis, high biocompatibility and flexibility as well as enhanced functionality compared to PEO. In this study, we present a quick and well-controlled synthesis of poly(butylene oxide)-block-poly(glycidol) (PBO-b-PG) amphiphilic diblock copolymers together with a straight-forward self-assembly protocol. Depending on the hydrophilic mass fraction of the copolymer, nanoscopic micelles, worms and polymersomes were formed as well as microscopic giant unilamellar vesicles. The particles were analysed regarding their size and shape, using dynamic and static light scattering, TEM and Cryo-TEM imaging as well as confocal laser scanning microscopy. We have discovered a strong dependence of the formed morphology on the self-assembly method and show that only solvent exchange leads to the formation of homogenous phases. Thus, a variety of different structures can be obtained from a highly flexible copolymer, justifying a potential use in biomedical applications. This journal is © The Royal Society of Chemistry.
- ItemA Polymer for Application as a Matrix Phase in a Concept of In Situ Curable Bioresorbable Bioactive Load-Bearing Continuous Fiber Reinforced Composite Fracture Fixation Plates(Basel : MDPI, 2021) Plyusnin, Artem; He, Jingwei; Elschner, Cindy; Nakamura, Miho; Kulkova, Julia; Spickenheuer, Axel; Scheffler, Christina; Lassila, Lippo V. J.; Moritz, NikoThe use of bioresorbable fracture fixation plates made of aliphatic polyesters have good potential due to good biocompatibility, reduced risk of stress-shielding, and eliminated need for plate removal. However, polyesters are ductile, and their handling properties are limited. We suggested an alternative, PLAMA (PolyLActide functionalized with diMethAcrylate), for the use as the matrix phase for the novel concept of the in situ curable bioresorbable load-bearing composite plate to reduce the limitations of conventional polyesters. The purpose was to obtain a preliminary understanding of the chemical and physical properties and the biological safety of PLAMA from the prospective of the novel concept. Modifications with different molecular masses (PLAMA-500 and PLAMA-1000) were synthesized. The efficiency of curing was assessed by the degree of convergence (DC). The mechanical properties were obtained by tensile test and thermomechanical analysis. The bioresorbability was investigated by immersion in simulated body fluid. The biocompatibility was studied in cell morphology and viability tests. PLAMA-500 showed better DC and mechanical properties, and slower bioresorbability than PLAMA-1000. Both did not prevent proliferation and normal morphological development of cells. We concluded that PLAMA-500 has potential for the use as the matrix material for bioresorbable load-bearing composite fracture fixation plates.
- ItemAnomalous influence of salt concentration on deposition of poly(L-lysine)/cellulose sulfate multilayers evidenced by in situ ATR-FTIR(Basel : MDPI, 2020) Müller, MartinThe deposition of polyelectrolyte (PEL) multilayers (PEMs) of poly(L-lysine)/cellulose sulfate (PLL/CS) onto germanium (Ge) substrates depending on salt concentration (cS) and deposition step z at constant PEL concentration cPEL = 0.01 M and pH = 7.0 was studied. In situ ATR-FTIR spectroscopy was used for the quantitative determination of alternate PLL/CS deposition profiles (adsorbed amount versus z) and total deposited PEM amount. By varying cS from 0 M to 1.0 M, a maximum of deposited amount was obtained at 0.1 M, so that both no salinity (0 M) and high salinity (1.0 M) revealed deposited amounts that were far lower than for mean salinity (0.1 M). Furthermore, in situ ATR-FTIR allowed to determine the detailed modulation of the PEL composition during the consecutive PEM deposition, which was interpreted as being due to both diffusion of given PEL from the PEM interior towards the outermost region and release of the PEM upon contact with the bulk oppositely charged PEL solution. Finally, ex situ ATR-FTIR measurements on the PEL solutions after deposition of PEM-20 revealed the distinct release of PEL from the PEM solely for cS = 1.0 M, due to the highest mobility of PEL under high salt conditions. These studies help to prepare functional PEM coatings with defined thicknesses and morphologies for the passivation and activation of material surfaces in the biomedical and food field. © 2020 by the author.
- ItemOn the Influence of Viscoelastic Modeling in Fluid Flow Simulations of Gum Acrylonitrile Butadiene Rubber(Basel : MDPI, 2021) Stieger, Sebastian; Mitsoulis, Evan; Walluch, Matthias; Ebner, Catharina; Kerschbaumer, Roman Christopher; Haselmann, Matthias; Mostafaiyan, Mehdi; Kämpfe, Markus; Kühnert, Ines; Wießner, Sven; Friesenbichler, WalterComputational fluid dynamics (CFD) simulation is an important tool as it enables engineers to study different design options without a time-consuming experimental workload. However, the prediction accuracy of any CFD simulation depends upon the set boundary conditions and upon the applied rheological constitutive equation. In the present study the viscoelastic nature of an unfilled gum acrylonitrile butadiene rubber (NBR) is considered by applying the integral and time-dependent Kaye–Bernstein–Kearsley–Zapas (K-BKZ) rheological model. First, exhaustive testing is carried out in the linear viscoelastic (LVE) and non-LVE deformation range including small amplitude oscillatory shear (SAOS) as well as high pressure capillary rheometer (HPCR) tests. Next, three abrupt capillary dies and one tapered orifice die are modeled in Ansys POLYFLOW. The pressure prediction accuracy of the K-BKZ/Wagner model was found to be excellent and insensitive to the applied normal force in SAOS testing as well as to the relation of first and second normal stress differences, provided that damping parameters are fitted to steady-state rheological data. Moreover, the crucial importance of viscoelastic modeling is proven for rubber materials, as two generalized Newtonian fluid (GNF) flow models severely underestimate measured pressure data, especially in contraction flow-dominated geometries.
- ItemIn situ preparation of crosslinked polymer electrolytes for lithium ion batteries(Basel : MDPI, 2020) Röchow, Eike T.; Coeler, Matthias; Pospiech, Doris; Kobsch, Oliver; Mechtaeva, Elizaveta; Vogel, Roland; Voit, Brigitte; Nikolowski, Kristian; Wolter, MareikeSolid polymer electrolytes for bipolar lithium ion batteries requiring electrochemical stability of 4.5 V vs. Li/Li+ are presented. Thus, imidazolium-containing poly(ionic liquid) (PIL) networks were prepared by crosslinking UV-photopolymerization in an in situ approach (i.e., to allow preparation directly on the electrodes used). The crosslinks in the network improve the mechanical stability of the samples, as indicated by the free-standing nature of the materials and temperature-dependent rheology measurements. The averaged mesh size calculated from rheologoical measurements varied between 1.66 nm with 10 mol% crosslinker and 4.35 nm without crosslinker. The chemical structure of the ionic liquid (IL) monomers in the network was varied to achieve the highest possible ionic conductivity. The systematic variation in three series with a number of new IL monomers offers a direct comparison of samples obtained under comparable conditions. The ionic conductivity of generation II and III PIL networks was improved by three orders of magnitude, to the range of 7.1 × 10−6 S·cm−1 at 20 °C and 2.3 × 10−4 S·cm−1 at 80 °C, compared to known poly(vinylimidazolium·TFSI) materials (generation I). The transition from linear homopolymers to networks reduces the ionic conductivity by about one order of magnitude, but allows free-standing films instead of sticky materials. The PIL networks have a much higher voltage stability than PEO with the same amount and type of conducting salt, lithium bis(trifluoromethane sulfonyl)imide (LiTFSI). GII-PIL networks are electrochemically stable up to a potential of 4.7 V vs. Li/Li+, which is crucial for a potential application as a solid electrolyte. Cycling (cyclovoltammetry and lithium plating-stripping) experiments revealed that it is possible to conduct lithium ions through the GII-polymer networks at low currents. We concluded that the synthesized PIL networks represent suitable candidates for solid-state electrolytes in lithium ion batteries or solid-state batteries.
- ItemAB- Versus AA+BB-Suzuki Polycondensation: A Palladium/Tris(tert-butyl)phosphine Catalyst Can Outperform Conventional Catalysts(Weinheim : Wiley-VCH, 2020) Zhang, Kenan; Tkachov, Roman; Ditte, Kristina; Kiriy, Nataliya; Kiriy, Anton; Voit, BrigitteA Pd/Pt-Bu3 catalyst having bulky, electron-rich ligands significantly outperforms conventional “step-growth catalysts” Pd(PPh3)4 and Pd(Po-Tol3)3 in the Suzuki polycondensation of the AB-type arylene-based monomers, such as some of the substituted fluorenes, carbazoles, and phenylenes. In the AA+BB polycondensation, Pd/Pt-Bu3 also performs better under homogeneous reaction conditions, in combination with the organic base Et4NOH. The superior performance of Pd/Pt-Bu3 is discussed in terms of its higher reactivity in the oxidative addition step and inherent advantages of the intramolecular catalyst transfer, which is a key step joining catalytic cycles of the AB-polycondensation. These findings are applied to the synthesis of a carbazole-based copolymer designed for the use as a hole conductor in solution-processed organic light-emitting diodes. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.