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Seeded Growth Synthesis of Gold Nanotriangles: Size Control, SAXS Analysis, and SERS Performance
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.
Further Enhancement of Mechanical Properties of Conducting Rubber Composites Based on Multiwalled Carbon Nanotubes and Nitrile Rubber by Solvent Treatment
Post-treatment removal of dispersion agents from carbon nanotube/rubber composites can greatly enhance the mechanical properties by increasing the filler–matrix interaction. In this study, multiwall carbon nanotubes (MWNT) were dispersed in water by sonication and nonionic surfactant, octyl-phenol-ethoxylate was used as a dispersion agent. The dispersed MWNTs were incorporated in thermo-reactive acrylonitrile butadiene rubber (NBR) latex and nanocomposite films were prepared by solution casting. As a post-treatment, the surfactant was removed with acetone and films were dried in air. Dispersion quality of the colloid before casting was determined, and mechanical, electrical and thermal properties of the composites before and after the acetone post-treatment were studied. It was found that removal of dispersion agent increased the storage modulus of films between 160–300% in all samples. Relative enhancement was greater in samples with better dispersion quality, whereas thermal conductivity changed more in samples with smaller dispersion quality values. Electrical properties were not notably affected.
Electrolytic Surface Treatment for Improved Adhesion between Carbon Fibre and Polycarbonate
To achieve good mechanical properties of carbon fibre-reinforced polycarbonate composites, the fibre-matrix adhesion must be dialled to an optimum level. The electrolytic surface treatment of carbon fibres during their production is one of the possible means of adapting the surface characteristics of the fibres. The production of a range of tailored fibres with varying surface treatments (adjusting the current, potential, and conductivity) was followed by contact angle, inverse gas chromatography and X-ray photoelectron spectroscopy measurements, which revealed a significant increase in polarity and hydroxyl, carboxyl, and nitrile groups on the fibre surface. Accordingly, an increase in the fibre-matrix interaction indicated by a higher interfacial shear strength was observed with the single fibre pull-out force-displacement curves. The statistical analysis identified the correlation between the process settings, fibre surface characteristics, and the performance of the fibres during single fibre pull-out testing.
MreB filaments align along greatest principal membrane curvature to orient cell wall synthesis
MreB is essential for rod shape in many bacteria. Membrane-associated MreB filaments move around the rod circumference, helping to insert cell wall in the radial direction to reinforce rod shape. To understand how oriented MreB motion arises, we altered the shape of Bacillus subtilis. MreB motion is isotropic in round cells, and orientation is restored when rod shape is externally imposed. Stationary filaments orient within protoplasts, and purified MreB tubulates liposomes in vitro, orienting within tubes. Together, this demonstrates MreB orients along the greatest principal membrane curvature, a conclusion supported with biophysical modeling. We observed that spherical cells regenerate into rods in a local, self-reinforcing manner: rapidly propagating rods emerge from small bulges, exhibiting oriented MreB motion. We propose that the coupling of MreB filament alignment to shape-reinforcing peptidoglycan synthesis creates a locally-acting, self-organizing mechanism allowing the rapid establishment and stable maintenance of emergent rod shape.
The Influence of Salt Anions on Heavy Metal Ion Adsorption on the Example of Nickel
The biodegradable polysaccharide chitosan possesses protonated and natural amino groups at medium pH values and has therefore been used as an adsorbing material for nickel salts in water treatment. Nickel is a problematic heavy metal ion which can cause various diseases and disorders in living organisms. Here, we show the influence of oxyanions (e.g., nitrate and sulfate) to the adsorption of nickel ions. Hence, simultaneously we are addressing the increasing global problem of nitrate and sulfate ion pollution in groundwater and surface water. A series of adsorption experiments was carried out in order to determine (i) the adsorption equilibrium, (ii) the adsorption capacity in dependence on the initial nickel ion concentration, and (iii) the influence of the anion presented in solution for the adsorption capacity. Surface morphology of chitosan flakes before and after the adsorption process has been studied with SEM-EDX analysis. The chitosan flakes exhibited promising adsorption capacities of 81.9 mg·g−1 and 21.2 mg·g−1 for nickel (sulfate) and nickel (nitrate), respectively. The calculated values of Gibbs free energy change ΔG0 confirm the higher adsorption of nickel ions in presence of sulfate ions. Hence, higher anion valence leads to a higher adsorption capacity.
Cononsolvency Transition of Polymer Brushes: A Combined Experimental and Theoretical Study
In this study, the cononsolvency transition of poly(N-isopropylacrylamide) (PNiPAAm) brushes in aqueous ethanol mixtures was studied by using Vis-spectroscopic ellipsometry (SE) discussed in conjunction with the adsorption-attraction model. We proved that the cononsolvency transition of PNiPAAm brushes showed features of a volume phase transition, such as a sharp collapse, reaching a maximum decrease in thickness for a very narrow ethanol volume composition range of 15% to 17%. These observations are in agreement with the recently published preferential adsorption model of the cononsolvency effect.
Why Should the “Alternative” Method of Estimating Local Interfacial Shear Strength in a Pull-Out Test Be Preferred to Other Methods?
One of the most popular micromechanical techniques of determining the local interfacial shear strength (local IFSS, τd) between a fiber and a matrix is the single fiber pull-out test. The τd values are calculated from the characteristic forces determined from the experimental force–displacement curves using a model which relates their values to local interfacial strength parameters. Traditionally, the local IFSS is estimated from the debond force, Fd, which corresponds to the crack initiation and manifests itself by a “kink” in the force–displacement curve. However, for some specimens the kink point is hardly discernible, and the “alternative” method based on the post-debonding force, Fb, and the maximum force reached in the test, Fmax, has been proposed. Since the experimental force–displacement curve includes three characteristic points in which the relationship between the current values of the applied load and the crack length is reliably established, and, at the same time, it is fully determined by only two interfacial parameters, τd and the interfacial frictional stress, τf, several methods for the determination of τd and τf can be proposed. In this paper, we analyzed several theoretical and experimental force–displacement curves for different fiber-reinforced materials (thermoset, thermoplastic and concrete) and compared all seven possible methods of τd and τf calculation. It was shown that the “alternative” method was the most accurate and reliable one, while the traditional approach often yielded the worst results. Therefore, we proposed that the “alternative” method should be preferred for the experimental force–displacement curves analysis.
Enhanced Interfacial Shear Strength and Critical Energy Release Rate in Single Glass Fiber-Crosslinked Polypropylene Model Microcomposites
Continuous glass fiber-reinforced polypropylene composites produced by using hybrid yarns show reduced fiber-to-matrix adhesion in comparison to their thermosetting counterparts. Their consolidation involves no curing, and the chemical reactions are limited to the glass fiber surface, the silane coupling agent, and the maleic anhydride-grafted polypropylene. This paper investigates the impact of electron beam crosslinkable toughened polypropylene, alkylene-functionalized single glass fibers, and electron-induced grafting and crosslinking on the local interfacial shear strength and critical energy release rate in single glass fiber polypropylene model microcomposites. A systematic comparison of non-, amino-, alkyl-, and alkylene-functionalized single fibers in virgin, crosslinkable toughened and electron beam crosslinked toughened polypropylene was done in order to study their influence on the local interfacial strength parameters. In comparison to amino-functionalized single glass fibers in polypropylene/maleic anhydride-grafted polypropylene, an enhanced local interfacial shear strength (+20%) and critical energy release rate (+80%) were observed for alkylene-functionalized single glass fibers in electron beam crosslinked toughened polypropylene.
Blending In Situ Polyurethane-Urea with Different Kinds of Rubber: Performance and Compatibility Aspects
Specific physical and reactive compatibilization strategies are applied to enhance the interfacial adhesion and mechanical properties of heterogeneous polymer blends. Another pertinent challenge is the need of energy-intensive blending methods to blend high-tech polymers such as the blending of a pre-made hard polyurethane (-urea) with rubbers. We developed and investigated a reactive blending method to prepare the outstanding blends based on polyurethane-urea and rubbers at a low blending temperature and without any interfacial compatibilizing agent. In this study, the polyurethane-urea (PUU) was synthesized via the methylene diphenyl diisocyanate end-capped prepolymer and m-phenylene diamine based precursor route during blending at 100 °C with polar (carboxylated nitrile rubber (XNBR) and chloroprene rubber (CR)) and non-polar (natural rubber (NR), styrene butadiene rubber (sSBR), and ethylene propylene butadiene rubber (EPDM)) rubbers. We found that the in situ PUU reinforces the tensile response at low strain region and the dynamic-mechanical response up to 150 °C in the case of all used rubbers. Scanning electron microscopy reveals a stronger rubber/PUU interface, which promotes an effective stress transfer between the blend phases. Furthermore, energy filtered transmission electron microscopy (EFTEM) based elemental carbon map identifies an interphase region along the interface between the nitrile rubber and in situ PUU phases of this exemplary blend type.
Online Structural-Health Monitoring of Glass Fiber-Reinforced Thermoplastics Using Different Carbon Allotropes in the Interphase
An electromechanical response behavior is realized by nanostructuring the glass fiber interphase with different highly electrically conductive carbon allotropes like carbon nanotubes (CNT), graphene nanoplatelets (GNP), or conductive carbon black (CB). The operational capability of these multifunctional glass fibers for an online structural-health monitoring is demonstrated in endless glass fiber-reinforced polypropylene. The electromechanical response behavior, during a static or dynamic three-point bending test of various carbon modifications, shows qualitative differences in the signal quality and sensitivity due to the different aspect ratios of the nanoparticles and the associated electrically conductive network densities in the interphase. Depending on the embedding position within the glass fiber-reinforced composite compression, shear and tension loadings of the fibers can be distinguished by different characteristics of the corresponding electrical signal. The occurrence of irreversible signal changes during the dynamic loading can be attributed to filler reorientation processes caused by polymer creeping or by destruction of electrically conductive paths by cracks in the glass fiber interphase.