On the response to hygrothermal aging of pultruded FRPs used in the civil engineering sector

This paper presents the effects of hygrothermal aging on the durability of a pultruded flat sheet, immersed in distilled water at 25oC, 40oC, 60oC or 80oC for a period of 224 days. Elevated temperatures noticeably increase the moisture diffusion coefficient and moisture uptake behaviour. Measured changes in the tensile and in-plane shear mechanical properties were examined after 28, 56, 112 or 224 days. Tensile properties remained practically unaffected by aging whereas matrix dominated shear properties revealed an initial drop which was recovered to a substantial degree after further hygrothermal aging. Visco-elastic property changes due to the superimposing mechanisms of plasticization, additional cross-linking etc. were recorded. Scanning Electron Microscopy micrographs indicate that the fibre/matrix interface remained practically intact, even after the most aggressive hot/wet aging. X-Ray Energy Dispersive Spectroscopy analysis showed no chemical degradation incidents on the fibre reinforcement surfaces and infrared spectroscopy revealed superficial chemical alteration in the aging matrix. Optical microscopy revealed matrix cracking in samples aged at 80oC for 112 days. Lastly, Computed Tomography scans of un-aged material showed internal imperfections that undoubtedly enhanced moisture transport. After aging at 60oC for 112 days, Computed Tomography detected preferentially situated water pockets

Advanced cryo-tomography workflow developments - correlative microscopy, milling automation and cryo-lift-out

Cryo-electron tomography (cryo-ET) is a groundbreaking technology for 3D visualisation and analysis of biomolecules in the context of cellular structures. It allows structural investigations of single proteins as well as their spatial arrangements within the cell. Cryo-tomograms provide a snapshot of the complex, heterogeneous and transient subcellular environment. Due to the excellent structure preservation in amorphous ice, it is possible to study interactions and spatial relationships of proteins in their native state without interference caused by chemical fixatives or contrasting agents. With the introduction of focused ion beam (FIB) technology, the preparation of cellular samples for electron tomography has become much easier and faster. The latest generation of integrated FIB and scanning electron microscopy (SEM) instruments (dual beam microscopes), specifically designed for cryo-applications, provides advances in automation, imaging and the preparation of high-pressure frozen bulk samples using cryo-lift-out technology. In addition, correlative cryo-fluorescence microscopy provides cellular targeting information through integrated software and hardware interfaces. The rapid advances, based on the combination of correlative cryo-microscopy, cryo-FIB and cryo-ET, have already led to a wealth of new insights into cellular processes and provided new 3D image data of the cell. Here we introduce our recent developments within the cryo-tomography workflow, and we discuss the challenges that lie ahead. Lay Description This article describes our recent developments for the cryo-electron tomography (cryo-ET) workflow. Cryo-ET offers superior structural preservation and provides 3D snapshots of the interior of vitrified cells at molecular resolution. Before a cellular sample can be imaged by cryo-ET, it must be made accessible for transmission electron microscopy. This is achieved by preparing a 200-300 nm thin cryo-lamella from the cellular sample using a cryo-focused ion beam (cryo-FIB) microscope. Cryo-correlative light and electron microscopy (cryo-CLEM) is used within the workflow to guide the cryo-lamella preparation to the cellular areas of interest. We cover a basic introduction of the cryo-ET workflow and show new developments for cryo-CLEM, which facilitate the connection between the cryo-light microscope and the cryo-FIB. Next, we present our progress in cryo-FIB software automation to streamline cryo-lamella preparation. In the final section we demonstrate how the cryo-FIB can be used for 3D imaging and how bulk-frozen cellular samples (obtained by high-pressure freezing) can be processed using the newly developed cryo-lift-out technology

Interactions between an aryl thioacetate-functionalized Zn(II) porphyrin and graphene oxide

The surface modification of graphene oxide (GO) is carried out via the supramolecular functionalization route using a Zn(II)-porphyrin which is soluble in common organic solvents on basis of long alkyl chains present at the exocyclic positions. This acts as a dispersing agent and decorates the surface of the graphene oxide uniformly, giving rise to a new nanohybrid denoted Zn(II)-porphyrin@GO. The resulting Zn(II)-porphyrin@GO nanohybrid forms a stable dispersion in ethanol (as characterized by several different spectroscopic techniques such as UV–vis, Fourier transform infrared, Raman). The morphology of Zn(II)-porphyrin@GO nanohybrid is investigated by atomic force microscopy (AFM) and transmission electron microscope (TEM)/selected area electron diffraction. Both TEM and AFM measurements indicate that the Zn(II)-porphyrin self-assemble onto the surface of graphene oxide sheets. Steady-state and time-resolved fluorescence emission studies in the dispersed phase, and as a thin film, point toward the strongly quenched fluorescence emission and lifetime decay, suggesting that energy transfer occurs from the singlet excited state of Zn(II)-porphyrin unit to GO sheets

Pico-electrochemistry in humidity-equilibrated electrolyte films on nano-cotton:Three- and four-point probe voltammetry and impedance

Cotton-extracted cellulose nanocrystals are spin-coated from aqueous suspension (0.6 wt%) onto glass slides to give ca. 40 nm thick films. Impregnation with LiCl and redox active Fe(CN)63−/4− into this film gives extremely thin redox active layers (typically 170 nm at 60% relative humidity), which were investigated with a 4-point or 3-point probe electrochemical system based on 250 μm diameter platinum wire probes. Both voltammetry and impedance measurements were performed and effects from humidity, concentrations, and time domain on measurements are reported. Only a pico-litre volume under the working electrode was “active” to give a novel electroanalytical “spot test”.publisher: Elsevier articletitle: Pico-electrochemistry in humidity-equilibrated electrolyte films on nano-cotton: Three- and four-point probe voltammetry and impedance journaltitle: Sensors and Actuators B: Chemical articlelink: http://dx.doi.org/10.1016/j.snb.2015.01.004 content_type: article copyright: Copyright © 2015 Elsevier B.V. All rights reserved.status: publishe

Shedding Light Onto the Nature of Iron Decorated Graphene and Graphite Oxide Nanohybrids for CO₂ Conversion at Atmospheric Pressure

We report on the design and testing of new graphite and graphene oxide‐based extended π‐conjugated synthetic scaffolds for applications in sustainable chemistry transformations. Nanoparticle‐functionalised carbonaceous catalysts for new Fischer Tropsch and Reverse GasWater Shift (RGWS) transformations were prepared: functional graphene oxides emerged from graphite powders via an adapted Hummer's method and subsequently impregnated with uniform‐sized nanoparticles. Then the resulting nanomaterials were imaged by TEM, SEM, EDX, AFM and characterised by IR, XPS and Raman spectroscopies prior to incorporation of Pd(II) promoters and further microscopic and spectroscopic analysis. Newly synthesised 2D and 3D layered nanostructures incorporating carbon‐supported iron oxide nanoparticulate pre‐catalysts were tested, upon hydrogen reduction in situ, for the conversion of CO2 to CO as well as for the selective formation of CH4 and longer chain hydrocarbons. The reduction reaction was also carried out and the catalytic species isolated and fully characterised. The catalytic activity of a graphene oxide‐supported iron oxide pre‐catalyst converted CO2 into hydrocarbons at different temperatures (305, 335, 370 and 405 °C), and its activity compared well with that of the analogues supported on graphite oxide, the 3‐dimensional material precursor to the graphene oxide. Investigation into the use of graphene oxide as a framework for catalysis showed that it has promising activity with respect to reverse gas water shift (RWGS) reaction of CO2 to CO, even at the low levels of catalyst used and under the rather mild conditions employed at atmospheric pressure. Whilst the γ‐Fe2O3 decorated graphene oxide‐based pre‐catalyst displays fairly constant activity up to 405 °C, it was found by GC‐MS analysis to be unstable with respect to decomposition at higher temperatures. The addition of palladium as a promoter increased the activity of the iron functionalised graphite oxide in the RWGS. The activity of graphene oxide supported catalysts was found to be enhanced with respect to that of iron‐functionalised graphite oxide with, or without palladium as a promoter, and comparable to that of Fe@carbon nanotube‐based systems tested under analogous conditions. These results display a significant step forward for the catalytic activity estimations for the iron functionalised and rapidly processable and scalable graphene oxide. The hereby investigated phenomena are of particular relevance for the understanding of the intimate surface morphologies and the potential role of non‐covalent interactions in the iron oxide‐graphene oxide networks, which could inform the design of nano‐materials with performance in future sustainable catalysis applications

Magnetically enhanced plasma coating of nanostructures with ultrathin diamond-like carbon films

Coating using magnetically enhanced plasma deposition gives smooth diamond-like carbon films that increase hardness and wear resistance of nanostructures.</p

A Raman spectroscopic study of uranyl minerals from Cornwall, UK

Raman spectra have been collected using three excitation wavelengths for thirteen uranyl mineral samples, including novác̆ekite, and analysed.</p

Intrinsically microporous polymer retains porosity in vacuum thermolysis to electroactive heterocarbon

Vacuum carbonization of organic precursors usually causes considerable structural damage and collapse of morphological features. However, for a polymer with intrinsic microporosity (PIM-EA-TB with a Brunauer–Emmet–Teller (BET) surface area of 1027 m2g–1), it is shown here that the rigidity of the molecular backbone is retained even during 500 °C vacuum carbonization, yielding a novel type of microporous heterocarbon (either as powder or as thin film membrane) with properties between those of a conducting polymer and those of a carbon. After carbonization, the scanning electron microscopy (SEM) morphology and the small-angle X-ray scattering (SAXS) Guinier radius remain largely unchanged as does the cumulative pore volume. However, the BET surface area is decreased to 242 m2g–1, but microporosity is considerably increased. The new material is shown to exhibit noticeable electrochemical features including two pH-dependent capacitance domains switching from ca. 33 Fg–1 (when oxidized) to ca. 147 Fg–1 (when reduced), a low electron transfer reactivity toward oxygen and hydrogen peroxide, and a four-point-probe resistivity (dry) of approximately 40 MΩ/square for a 1–2 μm thick film