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A novel superhydrophobic/superoleophilic surface has been developed by direct surface condensation of dichloroxylene that results in a controlled coating of hyper-cross-linked polymers. Specifically, the coating was successfully applied to a melamine formaldehyde sponge and optimized by fine-tuning the reaction variables. The resulting hierarchical porous sorbents stabilized by polydimethylsiloxane exhibited an increased surface area, good physiochemical stability, high selectivity, and adsorption capacities for a variety of oils and solvents. The composite can separate oil in water emulsions with ultrahigh separation efficiency >99% over 10 cycles in liter-scale experiments, wherein the highest separation efficiency was as low as 2 ppm even with a short period of filtration, suggesting strong potential for oil/water separation and recovery.

In this study, the modification of leather surface by application of TiO2-SiO2-GLYMO (3-Glycidyloxypropyltrimethoxysilane) nanocomposite coating and plasma treatment with N2 gas activation is investigated by using Small and Wide Angle X-ray scattering methods. The protective properties were tried to be developed with TEOS and HMDSO polymers’ usage in the coating process by following and controlling nano scale structural changes. The main aim was the controls of nanoscaled surface modifications and determination of the best coating process by keeping natural structure of the leathers. These scattering methods were useful to investigate the coating effects on the PTLs (Plasma Treated Leathers)’ internal structures including collagen microfibers and nanofibers which are hierarchical structures of triple helix collagen. The main purpose of the work was investigate whether the structural change in the natural form of the leather is present or not in the molecular-nanoscopic and microscopic scales after the coating and the applied physico-bio-chemical processes. On the other hand, the successful protective coatings and surface modifications were determined with SAXS analyses by controlling the shape, size and distance distributions of the appeared nanoglobular aggregations. The observations of structural changes taking place within collagen fibrils as a result of surface modification provides new insight into the nature of finishing and informs future processing developments. © 2020, © 2020 Taylor & Francis.

Plant and animal surfaces have become a model for preparing special synthetic surfaces with low wettability, reflectivity, or antibacterial properties. Processes that lead to the creation of replicas of natural character use two-step imprinting methods. This article describes a technique of synthetic polymer surface preparation by the process of two-stage imprinting. The laboratory-prepared structure copies the original natural pattern at the micrometer and sub-micrometer levels, supplemented by a new substructure. The new substructure identified by the scanning electron microscope is created at the nanometer level during the technological process. The nanostructure is formed only under the conditions that a hierarchical structure forms the surface of the natural replicated pattern, the replication mold is from a soft elastomeric material, and the material for producing the synthetic surface is a polymer capable of crystallizing. A new nanometer substructure formation occurs when the polymer cools to standard laboratory temperature and atmospheric pressure.

Hierarchical silicon structures consisting of micropyramids and nanowire arrays are fabricated by two-step chemical etching processes aimed at achieving cost and time effectiveness constraints without using any expensive vacuum system or complicated lithography process. The hierarchical structures can suppress the average reflectance to as low as 4.3% from 300 to 1100 nm without causing poor minority carrier lifetimes, exhibiting excellent broadband light-harvesting abilities with minimal recombination losses, which is the key point to design high-performance nanostructured solar cells. By utilizing hierarchical structures in the practical solar cells application, the short-circuit current density (JSC) shows a significant enhancement from 21.5 to 28.7 mA/cm2, and the conversion efficiency is enhanced by a factor of 35%. Such a significant enhancement is attributed not only to the superior light harvesting achieved by hierarchical structures but also to the benefit of small electrical losses in the solar cells. Thus, the concept and technique presented in this paper open avenues for developing high-performance structure solar devices.

Hierarchical Zn-ZSM-5 photocatalyst structures were synthesized via a hydrothermal one-pot synthesis route using a double template. Activated attapulgite (Si-ATP) and zinc nitrate (Zn(NO3)2) precursors were used as silicon and zinc sources, respectively. The structural properties, morphology, photocatalytic activity and the texture properties of the synthesized Zn-ZSM-5 photocatalysts were investigated using X-ray diffraction (XRD), scanning electron microscope (SEM), diffracted ultraviolet–visible (UV–Vis) spectrometry (DRUV–Vis) and N2 adsorption/desorption, respectively. It was found that the composites exhibit a typical MFI framework structure, a hexahedral twin structure and typical UV absorption peaks at 292 nm and 246 nm, when the Zn/Si mole ratio reaches its optimum value of 1:100. The hierarchical nanocrystals exhibit a similar Brunauer–Emmett–Teller surface area (309 m2 g−1) and a high mesopore ratio (37.47%) as compared to commercial zeolites. Sub-nano-sized zinc oxide (ZnO) particles with small size moieties were implanted and isolated in the silica matrices of micro-mesoporous zeolite, which had a significant photocatalytic activity and reusability of degrading methylene blue (MB) dyeing wastewater. Using a 500 W mercury lamp with the wavelength range from 185–500 nm operating during an illumination time of 30 min, the concentration of MB decreases significantly in the presence of Zn-ZSM-5 photocatalyst leading to a 95.56% of degradation, where the ratio still remained at 94.32% after six times of reuse.

International audience; The use of plant proteins to design colloidal food systems is a hot topic in the current context of the protein transition. However, replacing animal-derived proteins (in particular, dairy proteins) that have been traditionally used for this purpose by plant proteins is a challenge from various perspectives, and in particular, because of drastically different solubility and functionality. A possible route to mitigate these issues is to combine plant and dairy proteins, providing that their interactions can be understood from the molecular to the macroscopic scale. This review addresses the major advances that have occurred in the field of such blend-based systems, all the way from their behaviour in aqueous dispersions to their potential applications in gels, foams and emulsions.

We report the design and fabrication by laser direct writing via two photons polymerization of innovative hierarchical structures with cell-repellency capability. The structures were designed in the shape of “mushrooms”, consisting of an underside (mushroom’s leg) acting as a support structure and a top side (mushroom’s hat) decorated with micro- and nanostructures. A ripple-like pattern was created on top of the mushrooms, over length scales ranging from several µm (microstructured mushroom-like pillars, MMP) to tens of nm (nanostructured mushroom-like pillars, NMP). The MMP and NMP structures were hydrophobic, with contact angles of (127 ± 2)° and (128 ± 4)°, respectively, whereas flat polymer surfaces were hydrophilic, with a contact angle of (43 ± 1)°. The cell attachment on NMP structures was reduced by 55% as compared to the controls, whereas for the MMP, a reduction of only 21% was observed. Moreover, the MMP structures preserved the native spindle-like with phyllopodia cellular shape, whereas the cells from NMP structures showed a round shape and absence of phyllopodia. Overall, the NMP structures were more effective in impeding the cellular attachment and affected the cell shape to a greater extent than the MMP structures. The influence of the wettability on cell adhesion and shape was less important, the cellular behavior being mainly governed by structures’ topography.

Atomically precise ligand-protected nanoclusters (NCs) constitute an important class of compounds that exhibit well-defined structures and, when sufficiently small, evident molecular properties. NCs provide versatile building blocks to fabricate hierarchical superstructures. The assembly of NCs indeed offers opportunities to devise new materials with given structures and able to carry out specific functions. In this Concept article, we highlight the possibilities offered by NCs in which the physicochemical properties are controlled by the introduction of foreign metal atoms and/or modification of the composition of the capping monolayer with functional ligands. Different approaches to assemble NCs into dimers and higher hierarchy structures and the corresponding changes in physicochemical properties are also described.

Biophysical factors such as anisotropic topography composed of micro/nanosized structures are important for directing the fate of human bone marrow-derived mesenchymal stem cells (hBM-MSCs) and have been applied to neuronal differentiation. Via high-throughput screening (HTS) methods based on topography gradients, the optimum topography is determined and translated toward a hierarchical architecture designed to mimic the nerve nano/microstructure. The polydimethylsiloxane (PDMS)-based topography gradient with amplitudes (A) from 541 to 3073 nm and wavelengths (W) between 4 and 30 µm is developed and the fate commitment of MSC toward neuron lineage is investigated. The hierarchical structures, combining nano- and microtopography (W0.3/W26 parallel/perpendicular) are fabricated to explore the combined topography effects on neuron differentiation. From the immunofluorescent staining results (Tuj1 and MAP2), the substrate characterized by W: 26 µm; A: 2.9 µm shows highest potential for promoting neurogenesis. Furthermore, the hierarchical features (W0.3/W26 parallel) significantly enhance neural differentiation. The hBM-MSCs on the hierarchical substrates exhibit a significantly lower percentage of nuclear Yes-associated protein (YAP)/TAZ and weaker cell contractility indicating that the promoted neurogenesis is mediated by the cell tension and YAP/TAZ pathway. This research provides new insight into designing biomaterials for applications in neural tissue engineering and contributes to the understanding of topography-mediated neuronal differentiation.

International audience; Failure mechanisms associated with silicon‐based anodes are limiting the implementation of high‐capacity lithium‐ion batteries. Understanding the aging mechanism that deteriorates the anode performance and introducing novel‐architectured composites offer new possibilities for improving the functionality of the electrodes. Here, the characterization of nano‐architectured composite anode composed of active amorphous silicon domains (a‐Si, 20 nm) and crystalline iron disilicide (c‐FeSi2, 5–15 nm) alloyed particles dispersed in a graphite matrix is reported. This unique hierarchical architecture yields long‐term mechanical, structural, and cycling stability. Using advanced electron microscopy techniques, the nanoscale morphology and chemical evolution of the active particles upon lithiation/delithiation are investigated. Due to the volumetric variations of Si during lithiation/delithiation, the morphology of the a‐Si/c‐FeSi2 alloy evolves from a core‐shell to a tree‐branch type structure, wherein the continuous network of the active a‐Si remains intact yielding capacity retention of 70% after 700 cycles. The root cause of electrode polarization, initial capacity fading, and electrode swelling is discussed and has profound implications for the development of stable lithium‐ion batteries.

Made available in DSpace on 2018-11-29T12:37:12Z (GMT). No. of bitstreams: 0 Previous issue date: 2017-01-01. Added 1 bitstream(s) on 2019-10-09T18:27:34Z : No. of bitstreams: 1 S1516-14392017000800842.pdf: 3614732 bytes, checksum: d77bf6d3c6073fcae24ced575e5a0a2c (MD5) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Cellulose is a polymer widely available in nature, however its applications may be restrict due to its hydrophilic character. The creation of hierarchical structures on the surface is one of the required factors to obtain the hydrophobicity of this material. In order to compare the morphological and chemical effects caused by the action of different gases in the creation of nanostructures on the cellulose surface, samples were exposed to oxygen (O-2) and sulfur hexafluoride (SF6) plasma treatments. The changes in morphology after treatment prove that both the gases were able to create similar nanostructures in the material. The analysis of elemental composition and identification of functional groups on the sample surface showed that chemical modifications occurred differently for each treatment. Contact angle measurements revealed that samples treated by O-2 plasma remained hydrophilic, whereas low receptivity to polar (theta > 120 degrees) and non- polar (theta > 100 degrees) liquids was observed for samples exposed to SF6 plasma. Univ Fed Sao Carlos, Ctr Ciencias & Tecnol Sustentabilidade, Rod Joao Leme dos Santos,Km 110, BR-18052780 Sorocaba, SP, Brazil Univ Estadual Paulista, Lab Plasmas Tecnol, Campus Expt Sorocaba,Av Tres de Marco 511, BR-18087180 Sorocaba, SP, Brazil Univ Estadual Paulista, Lab Plasmas Tecnol, Campus Expt Sorocaba,Av Tres de Marco 511, BR-18087180 Sorocaba, SP, Brazil

application/pdf, Article, Journal of Materials Science. 2017, 52 (19), p.11229-11250

The formation of micropatterns combining nanostructured (porous) Si (NPSi) and bulk Si is induced by a sequential process of selective high energy ion irradiation and anodic etching. In this work, we investigate the microstructural origin of the increase of Si resistivity on irradiated areas, which is responsible for the inhibition of NPSi formation upon anodization. The increase of Si resistivity after irradiation at variable fluence has been evidenced from current voltage (I-V) characteristics. Microstructural aspects of the Si interfaces irradiated with 1.5–20 MeV Si ions have been revealed by elastic backscattering experiments in channeling configuration, Raman spectroscopy and high resolution transmission electron microscopy. It is concluded that inhibition of NPSi formation is induced at fluences that do not imply amorphization. In fact, the analysis of electrochemical capacitance-voltage measurements suggests that, at fluences well below the threshold for lattice disruption, the concentration of holes suffers from a drastic decrease at depths that match the location of maximum damage yield of the implanted Si ions. These results suggest that the mechanism responsible of formation of hierarchical Si structures is the local B dopant deactivation in the irradiated areas.https://doi.org/10.1016/j.vacuum.2016.10.011, This research was partially funded through grant MAT2014-54826- C2-1- R from Ministerio de Economía y Competitividad.

We demonstrate exceptionally large modulation of PL intensity in hierarchical titanium dioxide (TiO2) nanostructures exposed to molecular oxygen (O2). Optical responsivities up to about 1100% at 20% O2 concentrations are observed in hyperbranched anatase-phase hierarchical structures, outperforming those obtainable by commercial TiO2 nanopowders (up to a factor of ∼7 for response to synthetic air) and significantly improving the ones typically reported in PL-based opto-chemical gas sensing using MOXs. The improved PL response is discussed in terms of the specific morphology of hierarchical structures, characterized by simultaneous presence of small nanoparticles, large surface areas, and large voids. These characteristics guarantee an optimal interplay between photogenerated charges, PL-active centers, and adsorbed gas molecules. The results highlight the potentialities offered by hierarchical structures based on TiO2 or other MOXs and open interesting scenarios toward the development of all-optical and/or hybrid (opto/electrical) chemical sensors with improved sensitivity.

The direct assembly of functional nanoparticles into a highly crystalline mesoporous semiconductor with oriented configurations is challenging but of significance. Herein, an evaporation induced oriented co‐assembly strategy is reported to incorporate SnO2 nanocrystals (NCs) into a 3D branched mesoporous TiO2 framework by using poly(ethylene oxide)‐block‐polystyrene (PEO‐b‐PS) as the template, SnO2 NCs as the direct tin source, and titanium butoxide (TBOT) as the titania precursor. Owing to the combined properties of ultrasmall particle size (3–5 nm), excellent dispersibility and presence of abundant hydroxyl groups, SnO2 NCs can easily interact with PEO block of the template through hydrogen bonding and co‐assemble with hydrolyzed TBOT to form a novel hierarchical branched mesoporous structure (SHMT). After calcination, the obtained composites exhibit a unique 3D flower‐like structure, which consists of numerous mesoporous rutile TiO2 branches with uniform cylindrical mesopores (≈9 nm). More importantly, the SnO2 NCs are homogeneously distributed in the mesoporous TiO2 matrix, forming numerous n–n heterojunctions. Due to the unique textual structures, the SHMT‐based gas sensors show excellent gas sensing performance with fast response/recovery dynamics, high sensitivity, and selectivity toward ethanol.

The development of highly biomimetic scaffolds in terms of composition and structures, to repair or replace damaged bone tissues, is particularly relevant for tissue engineering. This paper investigates a 3D printed porous scaffold containing aligned multi-walled carbon nanotubes (MWCNTs) and nano-hydroxyapatite (nHA), mi- micking the natural bone tissue from the nanoscale to macroscale level. MWCNTs with similar dimensions as collagen fibres are coupled with nHA and mixed within a polycaprolactone (PCL) matrix to produce scaffolds using a screw-assisted extrusion-based additive manufacturing system. Scaffolds with different material com- positions were extensively characterised from morphological, mechanical and biological points of views. Transmission electron microscopy and polarised Raman spectroscopy confirm the presence of aligned MWCNTs within the printed filaments. The PCL/HA/MWCNTs scaffold are similar to the nanostructure of native bone and shows overall increased mechanical properties, cell proliferation, osteogenic differentiation and scaffold mi- neralisation, indicating a promising approach for bone tissue regeneration.

International audience; We report the fabrication of nanostructured microcantilevers employed as sensors for the detection of organophosphorus (OPs) vapors. These micromechanical sensors are prepared using a two-step procedure first optimized on a silicon wafer. TiO 2 one-dimensional nanostructures are synthesized at a silicon surface by a solvothermal method and then grafted with bifunctional molecules having an oxime group known for its strong affinity with organophosphorus compounds. The loading of oxime molecules grafted on the different nanostructured surfaces was quantified by UV spectroscopy. It has been found that a wafer covered by vertically aligned rutile TiO 2 nanorods (NRs), with an average length and width of 9.5 μm and 14.7 nm, respectively, provides an oxime function density of 360 nmol cm −2. The optimized TiO 2 nanorod synthesis was successfully reproduced on the cantilevers, leading to a homogeneous and reproducible TiO 2 NR film with the desired morphology. Thereafter, oxime molecules have been successfully grafted on the nanostructured cantilevers. Detection tests were performed in a dynamic mode by exposing the microcantilevers to dimethyl methylphosphonate (a model compound of toxic OPs agents) and following the shift of the resonant frequency. The nanostructure and the presence of the molecules on a TiO 2 NR surface both improve the response of the sensors. A detection limit of 2.25 ppm can be reached with this type of sensor.

Carbon-based materials have attracted intensive attentions for a wide range of energy and environment-related applications. Energy storage/conversion devices with improved performance have been achieved by utilization of metal-organic-framework (MOF)-derived carbon structures as active materials in recent years. However, the effects of MOF precursors on the performance of derived carbon materials are rarely investigated. Here, we report that the incorporation of small amount of Fe or Ni in Co-based MOFs leads to a significant enhancement for the derived carbon nanotube-based frameworks (CNTFs) in Na+/Cl- ion electrosorption. Further investigation revealed the enhanced performance can be attributed to the improved specific surface area, electrical conductivity, and electrochemical activity. Notably, the CoFe-CNTF derived from bimetallic CoFe-MOFs achieves a high ion adsorption capacity of 37.0 mg g-1, superior to most of recently reported carbon-based materials. Furthermore, the CoFe-CNTF also demonstrates high catalytic activity toward oxygen evolution reaction (OER) with a Tafel slope of 87.7 mV dec-1. After combination with three-dimensional graphene foam (3DG), the resultant CoFe-CNTF-coated 3DG is used as air-cathode to fabricate a flexible all-solid-state Zn-air battery, which exhibits a high open circuit potential of 1.455 V. Importantly, the fabricated flexible battery can light a light-emitting diode (LED) even when it is bent. This work provides new insights into designs of high-performance and flexible electrode based on MOF-derived materials.

Magnesium-based implants present several advantages for clinical applications, in particular due to their biocompatibility and degradability. However, degradation products can affect negatively the cell activity. In this work, a combined coating strategy to control the implant degradation and cell regulation processes is evaluated, including plasma electrolytic oxidation (PEO) that produces a 13 µm-thick Ca, P, and Si containing ceramic coating with surface porosity, and breath figures (BF) approach that produces a porous polymeric poly(ε-caprolactone) surface. The degradation of PCL-PEO-coated Mg hierarchical scaffold can be tailored to promote cell adhesion and proliferation into the porous structure. As a result, cell culture can colonize the inner PEO-ceramic coating structure where higher amount of bioelements are present. The Mg/PEO/PCL/BF scaffolds exhibit equally good or better premyoblast cell adhesion and proliferation compared with Ti CP control. The biological behavior of this new hierarchical functionalized scaffold can improve the implantation success in bone and cardiovascular clinical applications., This work was funded by ADITIMAT-CM Programme (S2018/NMT-4411) via Regional Government of Madrid and EU Structural Funds. A.S.-C. is grateful to Regional Government of Madrid and European Social Fund for financial support (PEJD-2018-POST/BMD-9592). The authors gratefully acknowledge financial support from the Spanish National Science Foundation (CSIC) and the Ministerio de Ciencia, Innovación y Universidades grant number MAT2016-78437-R, FONDOS FEDER

Developing novel anode materials containing electroactive heterostructures which boost ion and charge transfer kinetics in a carbon matrix is still a great challenge. Here we report on a new smartly designed material: SnS2/SnS p-n heterostructures embedded in S,N-doped carbon layer supported by hollow carbon spheres (C@SnSx@C) by a facile method and applied as negative electrode material in sodium ion batteries. The C@SnSx@C2 (at optimized carbon ratio) negative electrode can deliver an initial reversible capacity of 636.5 mAh·g−1 at 0.1 A·g−1, superior rate capability (265.1 mAh·g−1 at rate of 10.0 A·g−1) and long cycle life (capacity retention of 96.3 % at 1.0 A·g−1 after 150 cycles). The SnS2/SnS p-n heterojunctions provide a lower sodium ion diffusion energy barrier (0.38 eV), higher Na+ adsorption energy (−4.66 eV) and higher electronic conductivity due to an internal electric field according to density functional theory calculations compared to plain SnS. Moreover, S,N-doped carbon facilitates electronic conductivity and buffers the volume changes during the conversion reaction-based SnSx upon sodium insertion and extraction process. Porous hollow carbon spheres contribute to prevent the agglomeration of SnS2/SnS nanosheets and keep the structural integrity. Our findings on this unique material might be extended to other ion battery technologies.

Cellular structures (CSs) have been used extensively in recent years, as they offer a unique range of design freedoms. They can be deployed to create parts that can be lightweight by introducing controlled porous features, while still retaining or improving their mechanical, thermal, or even vibrational properties. Recent advancements in additive manufacturing (AM) technologies have helped to increase the feasibility and adoption of cellular structures. The layer-by-layer manufacturing approach offered by AM is ideal for fabricating CSs, with the cost of such parts being largely independent of complexity. There is a growing body of literature concerning CSs made via AM; this presents an opportunity to review the state-of-the-art in this domain and to showcase opportunities in design and manufacturing. This review will propose a novel way of classifying cellular structures by isolating their Geometrical Degrees of Freedom (GDoFs) and will explore the recent innovations in additively manufactured CSs. Based on the present work, the design inputs that are common in CSs generation will be highlighted. Furthermore, the work explores examples of how design inputs have been used to drive the design domain through various case studies. Finally, the review will highlight the manufacturability limitations of CSs in AM.

A facile route to hierarchically organized multicompartmentalized proteinosomes based on a recursive Pickering emulsion procedure using amphiphilic protein–polymer nanoconjugate building blocks is described. The number of incarcerated guest proteinosomes within a single host proteinosome is controlled, and enzymes and genetic polymers encapsulated within targeted subcompartments to produce chemically organized multi-tiered structures. Three types of spatiotemporal response—retarded concomitant release, synchronous release or hierarchical release of dextran and DNA—are demonstrated based on the sequential response of the host and guest membranes to attack by protease, or through variations in the positioning of disulfide-containing cross-links in either the host or guest proteinosomes integrated into the nested architectures. Overall, our studies provide a step towards the construction of hierarchically structured synthetic protocells with chemically and spatially integrated proto-organelles.

We introduce a new type of hybrid material: a nanostructured elastomer covered by a hard photoactive metal-oxide thin film resembling the exoskeleton of insects. It has extreme water repellency and fast self-recovery after damage. A new fabrication method for replicating high aspect ratio, hierarchical re-entrant aluminum structures into polydimethylsiloxane (PDMS) is presented. The method is based on a protective titania layer deposited by atomic layer deposition (ALD) on the aluminum template. The ALD titania transfers to the elastomeric scaffold via sacrificial release etching. The sacrificial release method allows for high aspect ratio, even 100 μm deep and successful release of overhanging structures, unlike conventional peeling. The ALD titania conformally covers the 3D multihierarchical structures of the template and protects the polymer during the release etch. Afterwards it prevents the high aspect ratio nanostructures from elasticity based collapse. The resulting nanostructured hybrid PDMS/titania replicas display robust superhydrophobicity without any further fluoro-coating or modification. Their mechanical and thermal robustness results from a thick nanostructured elastomeric layer which is conformally covered by ceramic titania instead of a monolayer hydrophobic coating. We have demonstrated the durability of these replicas against mechanical abrasion, knife scratches, rubbing, bending, peel tape test, high temperature annealing, UV exposure, water jet impingement and long term underwater storage. Though the material loses its superhydrophobicity in oxygen plasma exposure, a fast recovery from superhydrophilic to superhydrophobic can be achieved after 20 min UV irradiation. UV-assisted recovery is correlated with the high photoactivity of ALD titania film. This novel hybrid material will be applicable to the large area superhydrophobic surfaces in practical outdoor applications.

The creation of a hierarchical interface between the carbon fiber (CF) and the epoxy resin matrix of fiber-reinforced polymer (CFRP) composites has become an effective strategy for introducing multifunctional properties. Although the efficacy of many hierarchical interfaces has been established in lab-scale, their production is not amenable to high-volume, continuous, cost effective fiber production, which is required for the large-scale commercialization of composites. This work investigates the use of commercially available CO2 laser as a means of nano-structuring the surface of carbon fiber (CF) tows in an incessant throughput procedure. Even though the single carbon fiber tensile strength measurements showed a decrease up to 68% for the exposed CFs, the electrical conductivity exhibited an increment up to 18.4%. Furthermore, results on laminates comprised of irradiated unidirectional CF cloth, demonstrated an enhancement in out of plane electrical conductivity up to 43%, while preserved the Mode-I interlaminar fracture toughness of the composite, showing the potential for multifunctionality. This work indicates that the laser-induced graphitization of the CF surface can act as an interface for fast and cost-effective manufacturing of multifunctional CFRP composite materials.

Super-hydrophobic natural surfaces usually have multiple levels of structure hierarchy. Here, we report on the effect of surface structure hierarchy for droplet evaporation. The two-level hierarchical structures studied comprise micro-pillars superimposed with nanograss. The surface design is fully scalable as structures used in this study are replicated in polypropylene by a fast roll-to-roll extrusion coating method, which allows effective thermoforming of the surface structures on flexible substrates. As one of the main results, we show that the hierarchical structures can withstand pinning of sessile droplets and remain super-hydrophobic for a longer time than their non-hierarchical counterparts. The effect is documented by recording the water contact angles of sessile droplets during their evaporation from the surfaces. The surface morphology is mapped by atomic force microscopy (AFM) and used together with the theory of Miwa et al. to estimate the degree of water impregnation into the surface structures. Finally, the different behavior during the droplet evaporation is discussed in the light of the obtained water impregnation levels.

Acetylene gas (C2H2) is one of the main arc discharge characteristic gases dissolved in power transformer oil. It is of great potential to monitor the fault gas on-line by applying gas sensor technology. In this paper, gas sensors based on nanorods and nanoneedles assembled hierarchical NiO structures have been prepared. Herein, we focus on investigate the relationship between the sizes of the assembling blocking units and gas sensing properties. It can be found that the addition of CTAB/EG plays a vital role in controlling the sizes of blocking unit and assembly manner of 3D hierarchical structures. A comparison study reveals that an enhanced gas sensing performance toward C2H2 for the sensor based on nanoneedle-assembled NiO flowers occurs over that of nanorod-assembled NiO. This enhancement could be ascribed to the larger specific area of needle-flower, which provides more adsorption and desorption sites for chemical reaction as well as effective diffusion channels for C2H2. Besides, a method of calculating the specific surface area without BET testing was presented to verify the results of gas sensing measurement. The possible growth mechanism and gas sensing mechanism were discussed. Such a synthesis way may open up an avenue to tailor the morphologies and control the sizes of blocking units of some other metal oxides and enhance their gas sensing performances.

© 2018 The Authors. Helvetica Chimica Acta Published by Wiley-VHCA AG. The self-assembly of molecular inorganic/organic hybrid building blocks into ordered hierarchical nanomaterials with a tunable morphology is an enormous challenge. Here, we describe the synthesis and characterization of a novel liquid crystalline hydrogen-bonding hepta(dimethylsiloxane) azobenzene carboxylic acid dimer. This inorganic/organic hybrid dimer forms sub-5 nm lamellar features in the bulk and at the liquid solid interface. When mixed with a complementary hydrogen-bonding disk-shaped small molecule, a columnar hexagonal phase is formed. When adding a block copolymer containing hydrogen bond-accepting moieties, a hierarchical nanostructured material is obtained with a hexagonal columnar arrangement perpendicular to lamellae super structure. Our supramolecular approach shows that hierarchical hybrid nanomaterials can be fabricated with controlled properties which is appealing for applications such as nanoporous materials, organic electronics, and nanolithography. ispartof: HELVETICA CHIMICA ACTA vol:101 issue:10 status: published

Wetting has been studied in various fields: chemical industry, automobile manufacturing, food companies, and even life sciences. In these studies, super-hydrophobic surfaces have been achieved through complex steps and processes. To realize super-hydrophobicity, however, we demonstrated a simple and single pass laser process for the fabrication of micro/nano hierarchical structures on the flexible polytetrafluoroethylene (PTFE, Teflon) surface. The fabricated hierarchical structures helped increase the hydrophobicity by augmenting the surface roughness and promoting air-trapping. In addition, we employed a low-cost and high-throughput replication process producing numerous polydimethylsiloxane (PDMS) replicas from the laser-processed PTFE film. Thanks to the anti-adhesive characteristics of PTFE and the elasticity of PDMS, the structure perfectly transferred to the replica without any mechanical failure. Moreover, our designed mesh patterns offered the possibility of large area applications through varying the process parameters (pitch, beam spot size, laser fluence, and scan speed). Even though mesh patterns had relatively large pitch (190 &mu, m), we were able to achieve high contact angle (&gt, 150&deg, ). Through pneumatically deformed structure, we clearly showed that the shape of the droplets on our laser-processed super-hydrophobic surface was spherical. Based on these outcomes, we can expect our single laser pulse exposure process can overcome many drawbacks and offer opportunities for advancing applications of the wetting phenomena.

The ability of a gecko to run rapidly across ceilings and up and down vertical walls is a striking example of the application of van der Waals interactions.

Materials with highly ordered molecular arrangements have the capacity to display unique properties derived from their nanoscale structure. Here, the synthesis and characterization of azobenzene (AZO)-functionalized siloxane oligomers of discrete length that form photoswitchable supramolecular materials are described. Specifically, synergy between phase segregation and azobenzene crystallization leads to the self-assembly of an exfoliated 2D crystal that becomes isotropic upon photoisomerization with UV light. Consequently, the material undergoes a rapid athermal solid-to-liquid transition which can be reversed using blue light due to the unexpectedly fast 2D crystallization that is facilitated by phase segregation. In contrast, enabling telechelic supramolecular polymerization through hydrogen bonding inhibits azobenzene crystallization, and nanostructured pastes with well-ordered morphologies are obtained based on phase segregation alone, thus demonstrating block copolymer-like behavior. Therefore, by tailoring the balance of self-assembly forces in the azobenzene-functionalized siloxane oligomers, fast and reversible phase-changing materials can be engineered with various mechanical properties for applications in photolithography or switchable adhesion to lubricant properties.

Hierarchical VOOH hollow spheres with low crystallinity composed of nanoparticles were prepared by a facile and template-free method, which involved a precipitation of precursor microspheres in aqueous solution at room temperature and subsequent hydrothermal reaction. Quasi-solid-state symmetric and asymmetric supercapacitor (SSC and ASC) devices were fabricated using hierarchical VOOH hollow spheres as the electrodes, and the electrochemical properties of the VOOH//VOOH SSC device and the VOOH//AC ASC device were studied by cyclic voltammetry (CV), galvanostatic charge–discharge (GCD) and electrochemical impedance spectroscopy (EIS). Results demonstrated that the electrochemical performance of the VOOH//AC ASC device was better than that of the VOOH//VOOH SSC device. After 3000 cycles, the specific capacitance of the VOOH//AC ASC device retains 83% of the initial capacitance, while the VOOH//VOOH SSC device retains only 7.7%. Findings in this work proved that hierarchical VOOH hollow spheres could be a promising candidate as an ideal electrode material for supercapacitor devices.

This review focuses on the synthesis and chemical sensing characterization of metal oxide heterostructures reported since 2012. Heterostructures exhibit strong interactions between closely packed interfaces, showing superior performances compared to single structures. Surface effects appear thanks to the magnification of nanostructures’ surface leading to an enhancement of surface related properties (the base of chemical sensors working mechanism). The combination of different metal oxides to form heterostructures further improves the selectivity and/or other important sensing parameters. A very large number of different morphologies and structures have been proposed, each one exhibiting peculiar sensing properties towards specific chemical compounds. Among the different preparation methodologies, a significant number has been performed by means of hydrothermal method. However, the combination of various fabrication methods seems a very efficient strategy to obtain metal oxide-based heterostructures with different morphologies and dimensions such as core-shell nanostructures, one-dimensional heterostructures, two-dimensional layered heterojunctions, and three-dimensional hierarchical heterostructures. Despite all extraordinary advances in both material science and nanotechnology and the results achieved with heterostructured chemical sensors, there are few points that still deserve further studies and investigations, such as possible diffusion across the junctions, reproducibility of the fabrication process, synergistic or catalytic effects among the materials forming the heterostructures and influence/stability of the contacts. Moreover, perfect control over their growth is mandatory for their application in commercial devices. Only a careful understanding of the growth and the interface properties could fill the existing gap between laboratory studies and real-world exploitation of these heterostructures.

ZnO hierarchical structure has been synthesis by using chemical routs method. Hydra zinc nitrate, oleic acid, ethanol was used as row materials for the chemical reaction in the presence of NaOH. The Reaction took place at room temperature under stirrer. The prepared ZnO powder is collected and mixed with PVA to make a proper paste, then the paste was screen-printed in 1 cm square pattern to make thick films. Afterwards, the films are annealed at 500 C˚ for an hour. The morphology, crystallinity and structural properties are studied by X-ray diffraction, the experimental pattern of the films show very fine peaks indicate a good crystallization, also the morphology of the films studied by atomic force microscope and field emission scanning electron microscope. The sensitivity of zinc oxide NRs films to 100 ppm vapor methanol, ethanol and NH3 gas as a function of working temperature. As evident, the sensitivity increases with the temperature and reaches a maximum value in correspondence of T = 200-300 °C. If the temperature increases again, the sensitivity decreases.

CuS nanostructures have been prepared by hydrothermal route using copper nitrate and thiourea as copper and sulfur precursors. Investigations were done to probe the effect of cationic surfactant viz. cetyl trimethyl ammonium bromide on the morphology of the products. Further studies have been done to know the influence of reaction time on the morphology of CuS nanostructures. Results demonstrated that the morphology of CuS was influenced by the reaction time and surfactant. X-ray diffraction pattern showed that the as-prepared CuS nanostructures were in pure hexagonal phase and UV-vis spectra reveal a strong absorption in the visible region of 400-800 nm. A detailed mechanism has been elucidated for the growth of CuS nanostructures. The photocatalytic activity was evaluated by the decolorization of methylene blue (MB) dye under visible-light irradiation and results showed that 87% of the dye was degraded. Thus the as-prepared CuS catalysts are highly promising materials for photocatalytic applications towards dye degradation. (C) 2013 Elsevier B.V. All rights reserved.