Sea Water Aging ofGlass Reinforced Composites:Shear Behaviour andDamage Modelling

International audienceThis paper presents results from a study of the wet aging of four thermoset resins and their [0°/90°] stitched glass fibre reinforced composites. The matrix resins are orthophthalic polyester, isophthalic polyester, vinyl ester and epoxy. Resins and composites were aged for 18 months, under three immersion conditions: 20°C sea water, 50°C sea water and 50°C distilled water. Tensile tests,on resins and at 45° to fibre direction of composites, both before and after aging enable the influence of matrix resin and aging medium on weight changes and matrix dominated property degradation to be evaluated. This has enabled a unique data set to be obtained. A large part of the shear property loss after aging is recovered after drying. An original application of damage mechanics parameters is used to quantify the changes in composite shear behaviour, in order to provide a more complete representation of the inelastic response

Designing All Graphdiyne Materials as Graphene Derivatives: Topologically Driven Modulation of Electronic Properties

Designing new 2D systems with tunable properties is an important subject for science and technology. Starting from graphene, we developed an algorithm to systematically generate 2D carbon crystals belonging to the family of graphdiynes (GDYs) and having different structures and sp/sp(2) carbon ratios. We analyze how structural and topological effects can tune the relative stability and the electronic behavior, to propose a rationale for the development of new systems with tailored properties. A total of 26 structures have been generated, including the already known polymorphs such as alpha-, beta-, and gamma-GDY. Periodic density functional theory calculations have been employed to optimize the 2D crystal structures and to compute the total energy, the band structure, and the density of states. Relative energies with respect to graphene have been found to increase when the values of the carbon sp/sp(2) ratio increase, following however different trends based on the peculiar topologies present in the crystals. These topologies also influence the band structure, giving rise to semiconductors with a finite band gap, zero-gap semiconductors displaying Dirac cones, or metallic systems. The different trends allow identifying some topological effects as possible guidelines in the design of new 2D carbon materials beyond graphene

Low-frequency modes in the Raman spectrum of sp-sp2 nanostructured carbon

A novel form of amorphous carbon with sp-sp2 hybridization has been recently produced by supersonic cluster beam deposition showing the presence in the film of both polyynic and cumulenic species [L. Ravagnan et al. Phys. Rev. Lett. 98, 216103 (2007)]. Here we present a in situ Raman characterization of the low frequency vibrational region (400-800 cm-1) of sp-sp2 films at different temperatures. We report the presence of two peaks at 450 cm-1 and 720 cm-1. The lower frequency peak shows an evolution with the variation of the sp content and it can be attributed, with the support of density functional theory (DFT) simulations, to bending modes of sp linear structures. The peak at 720 cm-1 does not vary with the sp content and it can be attributed to a feature in the vibrational density of states activated by the disorder of the sp2 phase.Comment: 15 pages, 5 figures, 1 tabl

Interface coupling in Au-supported MoS2–WS2 heterobilayers grown by pulsed laser deposition

Van der Waals heterostructures of transition metal dichalcogenides (TMDs) are promising systems for engineering functional layered 2D materials with tailored properties. In this work, we study the growth of WS2/MoS2 and MoS2/WS2 heterobilayers by pulsed laser deposition (PLD) under ultra-high vacuum conditions. Using Au(111) as growth substrate, we investigated the heterobilayer morphology and structure at the nanoscale by in-situ scanning tunneling microscopy. Our experiments show that the heterostructure growth can be controlled with high coverage and thickness sensitivity by tuning the number of laser pulses in the PLD process. Raman spectroscopy complemented our investigation, revealing the effect of the interaction with the metallic substrate on the TMD vibrational properties and a strong interlayer coupling between the MoS2 and WS2 layers. The transfer of the heterobilayers on a silica substrate via a wet etching process shows the possibility to decouple them from the native metallic substrate and confirms that the interlayer coupling is not substrate-dependent. This work highlights the potential of the PLD technique as a method to grow TMD heterostructures, opening to new perspectives in the synthesis of complex 2D layered materials

Fabrication and Characterization of Molybdenum Tips for Scanning Tunneling Microscopy and Spectroscopy

We present a method for the preparation of bulk molybdenum tips for scanning Tunneling Microscopy and Spectroscopy (STM - STS) and we assess their potential in performing high resolution imaging and local spectroscop by measurements on different single crystal surfaces in UHV, namely Au(111), Si(111)-7x7 and titanium oxide 2D ordered nanostructures supported on Au(111). The fabrication method is versatile and can be extended to other metals, e.g. cobalt

Bulk Cr tips for scanning tunneling microscopy and spin-polarized scanning tunneling microscopy

A simple, reliable method for preparation of bulk Cr tips for Scanning Tunneling Microscopy (STM) is proposed and its potentialities in performing high-quality and high-resolution STM and Spin Polarized-STM (SP-STM) are investigated. Cr tips show atomic resolution on ordered surfaces. Contrary to what happens with conventional W tips, rest atoms of the Si(111)-7x7 reconstruction can be routinely observed, probably due to a different electronic structure of the tip apex. SP-STM measurements of the Cr(001) surface showing magnetic contrast are reported. Our results reveal that the peculiar properties of these tips can be suited in a number of STM experimental situations

Morphology-driven electrical and optical properties in graded hierarchical transparent conducting Al:ZnO

Graded Al-doped ZnO layers, constituted by a mesoporous forest like system evolving into a compact transparent conductor, were synthesized by Pulsed Laser Deposition with different morphology to study the correlation with functional properties. Morphology was monitored by measuring the resulting surface roughness and its effects on electrical conductivity (especially carrier mobility, which significantly decreases with increasing roughness) allow to discuss the limitations in conduction mechanisms. Significant changes in light scattering capability due to variations in morphology are also investigated and discussed to study the correlation between morphology and functional properties.Comment: 11 pages, 4 figure

Iatrogenic nerve injury in primary and revision reverse total shoulder arthroplasty

INTRODUCTION Iatrogenic nerve injury in orthopedic surgery can impair functional outcomes. During the last years, a steady increase in the number of performed reverse total shoulder arthroplasties has been reported and complications associated with this procedure are continuously described. Neurological complications, however, remain underreported. The aims of this study were to calculate the incidence of iatrogenic nerve injury after primary and revision reverse total shoulder arthroplasty in a large patient cohort, as well as identify associated patient-and surgery-related risk factors. MATERIALS AND METHODS A retrospective review of our institution's internal Reverse Total Shoulder Arthroplasty (RTSA) database from September 2005 to December 2019 was undertaken and 34 patients with iatrogenic nerve injuries were identified, resulting in a neurological complication rate of 2.6%. Group comparisons between patients with nerve injuries (n = 34) and the remaining cohort without nerve injuries (n = 1275) were performed to identify patient- and surgery-related risk factors. RESULTS Of the 34 cases with iatrogenic nerve injury, damage to terminal nerve branches occurred in 21 patients, whereas a brachial plexus lesion was diagnosed in the other 13. Nerve revision surgery was necessary in four patients. At final follow-up 13 patients (45%) had residual motor deficits and 17 (59%) had residual sensory deficits. Higher numbers of previous surgeries of the affected shoulder correlated with subsequent nerve injury (p = 0.035). Operative time was significantly longer in patients, who developed a neurologic deficit, showing a correlation between duration of surgery and occurrence of nerve injury (p = 0.013). Patients with neurologic complications were significantly younger than patients without nerve damage (median 68 vs. 72 years, p = 0.017). CONCLUSIONS In specialists' hands reverse total shoulder arthroplasty is a rather safe procedure regarding the risk of neurologic injury. However, multiple previous surgeries of the affected shoulder increase the risk of neurological complications. Cases with post-operative neurologic compromise are rare and usually recover well, with few patients suffering long-term functional deficits from iatrogenic nerve injury. LEVEL OF EVIDENCE Level III, retrospective cohort study

Vibrational - Electrical Properties Relationship in Donor Doped TiO2 by Raman Spectroscopy

Transparent conducting TiO2, obtained by Nb or Ta doping of the anatase structure, is gaining increasing attention for the development of transparent electrodes. Usually, regardless the deposition technique, a crystallization process in reducing atmosphere is necessary to achieve large mobility; in addition, electrical and optical properties are also strongly sensitive to the oxygen deposition pressure. These facts reveal that the defect chemistry of donor doped TiO2 is not trivial and involves a strict interplay among extrinsic dopant atoms, oxygen vacancies and ‘electron killer’ defects such as Ti vacancies and O interstitials. We here present a Raman characterization of donor-doped TiO2 films synthesized under several deposition and post-annealing conditions, employing different doping levels and dopant elements (i.e. Ta and Nb). Correlations between structure, crystallinity, shift and width of Raman peaks and electrical properties are shown and discussed. In particular, a clear relationship between the shift of the Eg(1) anatase Raman mode and the charge carrier density is found, while the B1g(1) mode connected to Ti-Ti vibrations is significantly affected by the extrinsic doping level. In this complex framework Raman spectroscopy can provide an invaluable contribution towards understanding the material structure and its influence on the functional properties

Disclosing Early Excited State Relaxation Events in Prototypical Linear Carbon Chains

One-dimensional (1D) linear nanostructures comprising sp-hybridized carbon atoms, as derivatives of the prototypicalallotropeknown as carbyne, are predicted to possess outstanding mechanical,thermal, and electronic properties. Despite recent advances in theirsynthesis, their chemical and physical properties are still poorlyunderstood. Here, we investigate the photophysics of a prototypicalpolyyne (i.e., 1D chain with alternating single and triple carbonbonds) as the simplest model of finite carbon wire and as a prototypeof sp-carbon-based chains. We perform transient absorptionexperiments with high temporal resolution (<30 fs) on monodispersedhydrogen-capped hexayne H (C C)(6)Hsynthesized by laser ablation in liquid. With the support of computationalstudies based on ground state density functional theory (DFT) andexcited state time-dependent (TD)-DFT calculations, we provide a comprehensivedescription of the excited state relaxation processes at early timesfollowing photoexcitation. We show that the internal conversion froma bright high-energy singlet excited state to a low-lying singletdark state is ultrafast and takes place with a 200 fs time constant,followed by thermalization on the picosecond time scale and decayof the low-energy singlet state with hundreds of picoseconds timeconstant. We also show that the time scale of these processes doesnot depend on the end groups capping the sp-carbonchain. The understanding of the primary photoinduced events in polyynesis of key importance both for fundamental knowledge and for potentialoptoelectronic and light-harvesting applications of low-dimensionalnanostructured carbon-based materials