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Now showing 1 - 10 of 404
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    Conformations of a Long Polymer in a Melt of Shorter Chains: Generalizations of the Flory Theorem
    (Washington, DC : ACS, 2015) Lang, Michael; Rubinstein, Michael; Sommer, Jens-Uwe
    Large-scale simulations of the swelling of a long N-mer in a melt of chemically identical P-mers are used to investigate a discrepancy between theory and experiments. Classical theory predicts an increase of probe chain size R ∼ P–0.18 with decreasing degree of polymerization P of melt chains in the range of 1 < P < N1/2. However, both experiment and simulation data are more consistent with an apparently slower swelling R ∼ P–0.1 over a wider range of melt degrees of polymerization. This anomaly is explained by taking into account the recently discovered long-range bond correlations in polymer melts and corrections to excluded volume. We generalize the Flory theorem and demonstrate that it is in excellent agreement with experiments and simulations.
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    Seeded Growth Synthesis of Gold Nanotriangles: Size Control, SAXS Analysis, and SERS Performance
    (Washington, DC : Soc., 2018) Kuttner, Christian; Mayer, Martin; Dulle, Martin; Moscoso, Ana; López-Romero, Juan Manuel; Förster, Stephan; Fery, Andreas; Pérez-Juste, Jorge; Contreras-Cáceres, Rafael
    We studied the controlled growth of triangular prismatic Au nanoparticles with different beveled sides for surface-enhanced Raman spectroscopy (SERS) applications. First, in a seedless synthesis using 3-butenoic acid (3BA) and benzyldimethylammonium chloride (BDAC), gold nanotriangles (AuNTs) were synthesized in a mixture with gold nanooctahedra (AuNOCs) and separated by depletion-induced flocculation. Here, the influence of temperature, pH, and reducing agent on the reaction kinetics was initially investigated by UV–vis and correlated to the size and yield of AuNT seeds. In a second step, the AuNT size was increased by seed-mediated overgrowth with Au. We show for the first time that preformed 3BA-synthesized AuNT seeds can be overgrown up to a final edge length of 175 nm and a thickness of 80 nm while maintaining their triangular shape and tip sharpness. The NT morphology, including edge length, thickness, and tip rounding, was precisely characterized in dispersion by small-angle X-ray scattering and in dry state by transmission electron microscopy and field-emission scanning electron microscopy. For sensor purposes, we studied the size-dependent SERS performance of AuNTs yielding analytical enhancement factors between 0.9 × 104 and 5.6 × 104 and nanomolar limit of detection (10–8–10–9 M) for 4-mercaptobenzoic acid and BDAC. These results confirm that the 3BA approach allows the fabrication of AuNTs in a whole range of sizes maintaining the NT morphology. This enables tailoring of localized surface plasmon resonances between 590 and 740 nm, even in the near-infrared window of a biological tissue, for use as colloidal SERS sensing agents or for optoelectronic applications.
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    Protein-Assisted Assembly of Modular 3D Plasmonic Raspberry-like Core/Satellite Nanoclusters: Correlation of Structure and Optical Properties
    (Washington, DC : Soc., 2016) Höller, Roland P. M.; Dulle, Martin; Thomä, Sabrina; Mayer, Martin; Steiner, Anja Maria; Förster, Stephan; Fery, Andreas; Kuttner, Christian; Chanana, Munish
    We present a bottom-up assembly route for a large-scale organization of plasmonic nanoparticles (NPs) into three-dimensional (3D) modular assemblies with core/satellite structure. The protein-assisted assembly of small spherical gold or silver NPs with a hydrophilic protein shell (as satellites) onto larger metal NPs (as cores) offers high modularity in sizes and composition at high satellite coverage (close to the jamming limit). The resulting dispersions of metal/metal nanoclusters exhibit high colloidal stability and therefore allow for high concentrations and a precise characterization of the nanocluster architecture in dispersion by small-angle X-ray scattering (SAXS). Strong near-field coupling between the building blocks results in distinct regimes of dominant satellite-to-satellite and core-to-satellite coupling. High robustness against satellite disorder was proved by UV/vis diffuse reflectance (integrating sphere) measurements. Generalized multiparticle Mie theory (GMMT) simulations were employed to describe the electromagnetic coupling within the nanoclusters. The close correlation of structure and optical property allows for the rational design of core/satellite nanoclusters with tailored plasmonics and well-defined near-field enhancement, with perspectives for applications such as surface-enhanced spectroscopies.
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    Polypropylene/Layered Double Hydroxide Nanocomposites: Influence of LDH Intralayer Metal Constituents on the Properties of Polypropylene
    (Washington, DC : ACS Publications, 2017) Nagendra, Baku; Rosely, C. V. Sijla; Leuteritz, Andreas; Reuter, Uta; Gowd, E. Bhoje
    Sonication-assisted delamination of layered double hydroxides (LDHs) resulted in smaller-sized LDH nanoparticles (∼50-200 nm). Such delaminated Co-Al LDH, Zn-Al LDH, and Co-Zn-Al LDH solutions were used for the preparation of highly dispersed isotactic polypropylene (iPP) nanocomposites. Transmission electron microscopy and wide-angle X-ray diffraction results revealed that the LDH nanoparticles were well dispersed within the iPP matrix. The intention of this study is to understand the influence of the intralayer metal composition of LDH on the various properties of iPP/LDH nanocomposites. The sonicated LDH nanoparticles showed a significant increase in the crystallization rate of iPP; however, not much difference in the crystallization rate of iPP was observed in the presence of different types of LDH. The dynamic mechanical analysis results indicated that the storage modulus of iPP was increased significantly with the addition of LDH. The incorporation of different types of LDH showed no influence on the storage modulus of iPP. But considerable differences were observed in the flame retardancy and thermal stability of iPP with the type of LDH used for the preparation of nanocomposites. The thermal stability (50% weight loss temperature (T0.5)) of the iPP nanocomposite containing three-metal LDH (Co-Zn-Al LDH) is superior to that of the nanocomposites made of two-metal LDH (Co-Al LDH and Zn-Al LDH). Preliminary studies on the flame-retardant properties of iPP/LDH nanocomposites using microscale combustion calorimetry showed that the peak heat release rate was reduced by 39% in the iPP/Co-Zn-Al LDH nanocomposite containing 6 wt % LDH, which is higher than that of the two-metal LDH containing nanocomposites, iPP/Co-Al LDH (24%) and iPP/Zn-Al LDH (31%). These results demonstrated that the nanocomposites prepared using three-metal LDH showed better thermal and flame-retardant properties compared to the nanocomposites prepared using two-metal LDH. This difference might be due to the better char formation capability of three-metal LDH compared to that of two-metal LDH.
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    Fe3O4 Nanoparticles Grown on Cellulose/GO Hydrogels as Advanced Catalytic Materials for the Heterogeneous Fenton-like Reaction
    (Washington, DC : ACS Publications, 2019) Chen, Yian; Pötschke, Petra; Pionteck, Jürgen; Voit, Brigitte; Qi, Haisong
    Cellulose/graphene oxide (GO)/iron oxide (Fe3O4) composites were prepared by coprecipitating iron salts onto cellulose/GO hydrogels in a basic solution. X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared, and X-ray diffraction characterization showed that Fe3O4 was successfully coated on GO sheets and cellulose. Cellulose/GO/Fe3O4 composites showed excellent catalytic activity by maintaining almost 98% of the removal of acid orange 7 (AO7) and showed stability over 20 consecutive cycles. This performance is attributable to the synergistic effect of Fe3O4 and GO during the heterogeneous Fenton-like reaction. Especially, the cellulose/GO/Fe3O4 composites preserve their activity by keeping the ratio of Fe3+/Fe2+ at 2 even after 20 catalysis cycles, which is supported by XPS analysis.
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    Devulcanization of Waste Rubber and Generation of Active Sites for Silica Reinforcement
    (Washington, DC : ACS Publications, 2019) Ghorai, Soumyajit; Mondal, Dipankar; Hait, Sakrit; Ghosh, Anik Kumar; Wiessner, Sven; Das, Amit; De, Debapriya
    Each year, hundreds of millions of tires are produced and ultimately disposed into nature. To address this serious environmental issue, devulcanization could be one of the sustainable solutions that still remains as one of the biggest challenges across the globe. In this work, sulfur-vulcanized natural rubber (NR) is mechanochemically devulcanized utilizing a silane-based tetrasulfide as a devulcanizing agent, and subsequently, silica (SiO2)-based rubber composites are prepared. This method not only breaks the sulfur–sulfur cross-links but also produces reactive poly(isoprene) chains to interact with silica. The silica natural rubber composites are prepared by replacing 30% fresh NR by devulcanized NR with varying contents of silica. The composites exhibit excellent mechanical properties, tear strength, abrasion resistance, and dynamic mechanical properties as compared with the fresh natural rubber silica composites. The tensile strength of devulcanized rubber-based silica composites is ∼20 MPa, and the maximum elongation strain is ∼921%. The devulcanized composites are studied in detail by chemical, mechanical, and morphological analyses. Thus, the value added by the devulcanized rubber could attract the attention of recycling community for its sustainable applications.
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    Influence of microwave plasma treatment on the surface properties of carbon fibers and their adhesion in a polypropylene matrix
    (London [u.a.] : Institute of Physics, 2016) Scheffler, C.; Wölfel, E.; Förster, T.; Poitzsch, C.; Kotte, L.; Mäder, G.; Madsen, Bo; Biel, A.; Kusano, Y.; Lilholt, H.; Mikkelsen, L.P.; Mishnaevsky Jr., L.; Sørensen, B.F.
    A commercially available carbon fiber (CF) with an epoxy-based sizing (EP-sized CF) and an unsized CF have been plasma treated to study the effect on the fiber-matrix adhesion towards a polypropylene matrix. The EP-sized fiber was chosen because of its predictable low adhesion in a polypropylene (PP) matrix. The fibers have been modified using a microwave low-pressure O2/CO2/N2-gas plasma source (Cyrannus®) developed at IWS in a batch process. One aim of this study was the evaluation of parameters using high energies and short time periods in the plasma chamber to see the effect on mechanical performance of CF. These results will be the fundamental work for a planned continuous plasma modification line. The CF surface was characterized by determining the surface energies, single fiber tensile strength and XPS analysis. The adhesion behavior before and after plasma treatment was studied by single fiber pull-out test (SFPO) and scanning electron microscopy (SEM). It was shown that the CO2- and O2-plasma increases the number of functional groups on the fiber surface during short time plasma treatment of 30 s. Carboxylic groups on the unsized CF surface resulting from O2-plasma treatment lead to an enhanced fiber-matrix adhesion, whereas the fiber strength was merely reduced.
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    Basic material and technology investigations for material bonded hybrids by continuous hybrid profile fabrication
    (London [u.a.] : Institute of Physics, 2021) Schubert, K.; Gedan-Smolka, M.; Marschner, A.; Rietzschel, T.; Uhlig, K.; Löpitz, D.; Wagner, D.; Knobloch, M.; Karjust, Krist; Otto, Tauno; Kübarsepp, Jakob; Hussainova, Irina
    The development of multi-material hybrids by injection molding has been studied very intensively at the IPF in the past. For that, a material bonding between the different substrates was achieved by using a newly developed two-step curing powder coating material as latent reactive adhesive. The aim of the project “Hybrid Pultrusion” was to perform a novel approach for the fabrication of material bonded metal-plastic joints (profiles) in a modified pultrusion process. Therefore, powder pre-coated steel coil is combined with a glass-fiber reinforced epoxy resin matrix. For initial basic studies, the impregnated fiber material has been applied on the pre-coated steel sheets using the Resin Transfer Molding process (RTM-process). It was proved via lap shear tests, that this procedure resulted in very high adhesive strengths up to 35 MPa resulting from the formation of a covalent matrix-steel bonding as well. In addition, the failure mechanism was subsequently studied. Furthermore, by adapting the successful material combination to the pultrusion process it was demonstrated that material bonded hybrids can be achieved even under these continuous processing conditions.
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    Effects of high energy electrons on the properties of polyethylene / multiwalled carbon nanotubes composites: Comparison of as-grown and oxygen-functionalised MWCNT
    (Melville, NY : AIP, 2014) Krause, Beate; Pötschke, Petra; Gohs, U.
    Polymer modification with high energy electrons (EB) is well established in different applications for many years. It is used for crosslinking, curing, degrading, grafting of polymeric materials and polymerisation of monomers. In contrast to this traditional method, electron induced reactive processing (EIReP) combines the polymer modification with high energy electrons and the melt mixing process. This novel reactive method was used to prepare polymer blends and composites. In this study, both methods were used for the preparation of polyethylene (PE)/ multiwalled carbon nanotubes (MWCNT) composites in the presence of a coupling agent. The influence of MWCNT and type of electron treatment on the gel content, the thermal conductivity, rheological, and electrical properties was investigated whereby as-grown and oxidised MWCNT were used. In the presence of a coupling agent and at an absorbed dose of 40 kGy, the gel content increased from 57 % for the pure PE to 74 % or 88 % by the addition of as-grown (Baytubes® C150P) or oxidised MWCNT, respectively. In comparison to the composites containing the as-grown MWCNTs, the use of the oxidised MWCNTs led to higher melt viscosity and higher storage modulus due to higher yield of filler polymer couplings. The melt viscosity increased due to the addition of MWCNT and crosslinking of PE. The thermal conductivity increased to about 150 % and showed no dependence on the kind of MWCNT and the type of electron treatment. In contrast, the lowest value of electrical volume resistivity was found for the non-irradiated samples and after state of the art electron treatment without any influence of the type of MWCNT. In the case of EIReP, the volume resistivity increased by 2 (as-grown MWCNT) or 3 decades (oxidised MWCNT) depending on the process parameters. © 2014 American Institute of Physics.
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    Melt mixed composites of polypropylene with singlewalled carbon nanotubes for thermoelectric applications: Switching from p- to n-type behavior by additive addition
    (Melville, NY : AIP, 2019) Pötschke; Petra; Krause, Beate; Luo, Jinji
    Composites were prepared with polypropylene (PP) as the matrix and singlewalled CNTs (SWCNTs) of the type TUBALL from OCSiAl Ltd. as the conducting component by melt processing in a small-scale twin-screw compounder. In order to switch the typical p-type behavior of such composites from positive Seebeck coefficients (S) into n-type behavior with negative Seebeck coefficients, a non-ionic surfactant polyoxyethylene 20 cetyl ether (Brij58) was used and compared with a PEG additive, which was shown previously to be able to induce such switching. For PP-2 wt% SWCNT composites Brij58 is shown to result in n-type composites. The negative S values (up to −48.2 µV/K) are not as high as in the case of previous results using PEG (−56.6 µV/K). However, due to the more pronounced effect of Brij58 on the electrical conductivity, the achieved power factors are higher and reach a maximum of 0.144 µW/(m·K2) compared to previous 0.078 µW/(m·K2) with PEG. Dispersion improvement depends on the type of SWCNTs obtained by using varied synthesis/treatment conditions. Solution prepared composites of PEG with SWCNTs also have negative S values, indicating the donation of electrons from PEG to the SWCNTs. However, such composites are brittle and not suitable as thermoelectric materials.