Sulfonated Pentablock Copolymer (NexarTM) for Water Remediation and Other Applications.

This review focuses on the use of a sulfonated pentablock copolymer commercialized as NexarTM in water purification applications. The properties and the use of sulfonated copolymers, in general, and of NexarTM, in particular, are described within a brief reference focusing on the problem of different water contaminants, purification technologies, and the use of nanomaterials and nanocomposites for water treatment. In addition to desalination and pervaporation processes, adsorption and photocatalytic processes are also considered here. The reported results confirm the possibility of using NexarTM as a matrix for embedded nanoparticles, exploiting their performance in adsorption and photocatalytic processes and preventing their dispersion in the environment. Furthermore, the reported antimicrobial and antibiofouling properties of NexarTM make it a promising material for achieving active coatings that are able to enhance commercial filter lifetime and performance. The coated filters show selective and efficient removal of cationic contaminants in filtration processes, which is not observed with a bare commercial filter. The UV surface treatment and/or the addition of nanostructures such as graphene oxide (GO) flakes confer NexarTM with coating additional functionalities and activity. Finally, other application fields of this polymer are reported, i.e., energy and/or gas separation, suggesting its possible use as an efficient and economical alternative to the more well-known Nafion polymer.

Impact of Doping on Cross-Sectional Stress Assessment of 3C-SiC/Si Heteroepitaxy.

In this paper, we used micro-Raman spectroscopy in cross-section to investigate the effect of different doping on the distribution of stress in the silicon substrate and the grown 3C-SiC film. The 3C-SiC films with a thickness up to 10 µm were grown on Si (100) substrates in a horizontal hot-wall chemical vapor deposition (CVD) reactor. To quantify the influence of doping on the stress distribution, samples were non-intentionally doped (NID, dopant incorporation below 1016 cm-3), strongly n-type doped ([N] > 1019 cm-3), or strongly p-type doped ([Al] > 1019 cm-3). Sample NID was also grown on Si (111). In silicon (100), we observed that the stress at the interface is always compressive. In 3C-SiC, instead, we observed that the stress at the interface is always tensile and remains so in the first 4 µm. In the remaining 6 µm, the type of stress varies according to the doping. In particular, for 10 µm thick samples, the presence of an n-doped layer at the interface maximizes the stress in the silicon (~700 MPa) and in the 3C-SiC film (~250 MPa). In the presence of films grown on Si(111), 3C-SiC shows a compressive stress at the interface and then immediately becomes tensile following an oscillating trend with an average value of 412 MPa.

Sulfonated Pentablock Copolymer Coating of Polypropylene Filters for Dye and Metal Ions Effective Removal by Integrated Adsorption and Filtration Process.

In this work, we coated polypropylene (PP) fibrous filters with sulfonated pentablock copolymer (s-PBC) layers and tested them for the removal of cationic organic dyes, such as methylene blue (MB), and heavy metal ions (Fe3+ and Co2+) from water by adsorption and filtration experiments. Some of the coated filters were irradiated by UV light before being exposed to contaminated water and then were tested with unirradiated filters in the same adsorption and filtration experiments. Polymer-coated filters showed high efficiency in removing MB from an aqueous solution in both absorption and filtration processes, with 90% and 80% removal, respectively. On the other hand, for heavy metal ions (Fe3+ and Co2+), the coated filters showed a better removal performance in the filtration process than for the adsorption one. In fact, in the adsorption process, controlled interaction times allow the ionic species to interact with the surface of the filters leading to the formation and release of new species in solution. During filtration, the ionic species are easily trapped in the filters, in particular by UV modified filters, and we observed for Fe3+ ions a total removal (>99%) in a single filtration process and for Co2+ ions a larger removal with respect to the untreated filter. The mechanisms involved in the removal of the contaminants processes were investigated by characterizing the filters before and after use by means of scanning electron microscopy (SEM) combined with energy-dispersive X-ray (EDX) analysis and Fourier transform infrared spectroscopy (FT-IR).

Impact of Nitrogen on the Selective Closure of Stacking Faults in 3C-SiC.

Despite the promising properties, the problem of cubic silicon carbide (3C-SiC) heteroepitaxy on silicon has not yet been resolved and its use in microelectronics is limited by the presence of extensive defects. In this paper, we used microphotoluminescence (µ-PL), molten KOH etching, and high-resolution scanning transmission electron microscopy (HRSTEM) to investigate the effect of nitrogen doping on the distribution of stacking faults (SFs) and assess how increasing dosages of nitrogen during chemical vapor deposition (CVD) growth inhibits the development of SFs. An innovative angle-resolved SEM observation approach of molten KOH-etched samples resulted in detailed statistics on the density of the different types of defects as a function of the growth thickness of 3C-SiC free-standing samples with varied levels of nitrogen doping. Moreover, we proceeded to shed light on defects revealed by a diamond-shaped pit. In the past, they were conventionally associated with dislocations (Ds) due to what happens in 4H-SiC, where the formation of pits is always linked with the presence of Ds. In this work, the supposed Ds were observed at high magnification (by HRSTEM), demonstrating that principally they are partial dislocations (PDs) that delimit an SF, whose development and propagation are suppressed by the presence of nitrogen. These results were compared with VESTA simulations, which allowed to simulate the 3C-SiC lattice to design two 3C-lattice domains delimited by different types of SFs. In addition, through previous experimental evidence, a preferential impact of nitrogen on the closure of 6H-like SFs was observed as compared to 4H-like SFs.

New Approaches and Understandings in the Growth of Cubic Silicon Carbide.

In this review paper, several new approaches about the 3C-SiC growth are been presented. In fact, despite the long research activity on 3C-SiC, no devices with good electrical characteristics have been obtained due to the high defect density and high level of stress. To overcome these problems, two different approaches have been used in the last years. From one side, several compliance substrates have been used to try to reduce both the defects and stress, while from another side, the first bulk growth has been performed to try to improve the quality of this material with respect to the heteroepitaxial one. From all these studies, a new understanding of the material defects has been obtained, as well as regarding all the interactions between defects and several growth parameters. This new knowledge will be the basis to solve the main issue of the 3C-SiC growth and reach the goal to obtain a material with low defects and low stress that would allow for realizing devices with extremely interesting characteristics.

Effect of Nitrogen and Aluminum Doping on 3C-SiC Heteroepitaxial Layers Grown on 4° Off-Axis Si (100).

This work provides a comprehensive investigation of nitrogen and aluminum doping and its consequences for the physical properties of 3C-SiC. Free-standing 3C-SiC heteroepitaxial layers, intentionally doped with nitrogen or aluminum, were grown on Si (100) substrate with different 4° off-axis in a horizontal hot-wall chemical vapor deposition (CVD) reactor. The Si substrate was melted inside the CVD chamber, followed by the growth process. Micro-Raman, photoluminescence (PL) and stacking fault evaluation through molten KOH etching were performed on different doped samples. Then, the role of the doping and of the cut angle on the quality, density and length distribution of the stacking faults was studied, in order to estimate the influence of N and Al incorporation on the morphological and optical properties of the material. In particular, for both types of doping, it was observed that as the dopant concentration increased, the average length of the stacking faults (SFs) increased and their density decreased.

Characterization of 4H- and 6H-Like Stacking Faults in Cross Section of 3C-SiC Epitaxial Layer by Room-Temperature µ-Photoluminescence and µ-Raman Analysis.

We report a comprehensive investigation on stacking faults (SFs) in the 3C-SiC cross-section epilayer. 3C-SiC growth was performed in a horizontal hot-wall chemical vapour deposition (CVD) reactor. After the growth (85 microns thick), the silicon substrate was completely melted inside the CVD chamber, obtaining free-standing 4 inch wafers. A structural characterization and distribution of SFs was performed by µ-Raman spectroscopy and room-temperature µ-photoluminescence. Two kinds of SFs, 4H-like and 6H-like, were identified near the removed silicon interface. Each kind of SFs shows a characteristic photoluminescence emission of the 4H-SiC and 6H-SiC located at 393 and 425 nm, respectively. 4H-like and 6H-like SFs show different distribution along film thickness. The reported results were discussed in relation with the experimental data and theoretical models present in the literature.

Optical and photocatalytic properties of TiO2 nanoplumes.

Here we report the photocatalytic efficiency of hydrogenated TiO2 nanoplumes studied by measuring dye degradation in water. Nanoplumes were synthesized by peroxide etching of Ti films with different thicknesses. Structural characterization was carried out by scanning electron microscopy and transmission electron microscopy. We investigated in detail the optical properties of the synthesized material and related them to the efficiency of UV photodegradation of methylene blue dye. The obtained results show that TiO2 nanoplumes act as an effective antireflective layer increasing the UV photocatalytic yield of the film.

Toxicity Evaluation of New Engineered Nanomaterials in Zebrafish.

The effect of the nanoparticles on the marine organisms, depends on their size, chemical composition, surface structure, solubility and shape. In order to take advantage from their activity, preserving the surrounding environment from a possible pollution, we are trying to trap the nanoparticles into new nanomaterials. The nanomaterials tested were synthesized proposing a ground-breaking approach by an upside-down vision of the Au/TiO2 nano-system to avoid the release of nanoparticles. The system was synthesized by wrapping Au nanoparticles with a thin layer of TiO2. The non-toxicity of the nano-system was established by testing the effect of the material on zebrafish larvae. Danio rerio o zebrafish was considered an excellent model for the environmental biomonitoring of aquatic environments and the Zebrafish Embryo Toxicity Test (ZFET) is considered an alternative method of animal test. For this reason zebrafish larvae were exposed to different concentrations of nanoparticles of TiO2 and Au and new nanomaterials. As biomarkers of exposure, we evaluated the expression of metallothioneins by immunohistochemistry analysis and western blotting analysis also. The results obtained by toxicity test showed that neither mortality as well as sublethal effects were induced by the different nanomaterials and nanoparticles tested. Only zebrafish larvae exposed to free Au nanoparticles showed a different response to anti-MT antibody. In fact, the immunolocalization analysis highlighted an increase of the metallothioneins synthesis.

TiO2-coated nanostructures for dye photo-degradation in water.

The photocatalytic efficiency of a thin-film TiO2-coated nanostructured template is studied by dye degradation in water. The nanostructured template was synthesized by metal-assisted wet etching of Si and used as substrate for the deposition of a thin film of TiO2 (10 nm thick) by atomic layer deposition. A complete structural characterization was made by scanning and transmission electron microscopies. The significant photocatalytic performance was evaluated by the degradation of two dyes in water: methylene blue and methyl orange. The relevance of the reported results is discussed, opening the route toward the application of the synthesized nanostructured TiO2 for water purification.

An enhanced photocatalytic response of nanometric TiO2 wrapping of Au nanoparticles for eco-friendly water applications.

We propose a ground-breaking approach by an upside-down vision of the Au/TiO2 nano-system in order to obtain an enhanced photocatalytic response. The system was synthesized by wrapping Au nanoparticles (∼8 nm mean diameter) with a thin layer of TiO2 (∼4 nm thick). The novel idea of embedding Au nanoparticles with titanium dioxide takes advantage of the presence of metal nanoparticles, in terms of electron trapping, without losing any of the TiO2 exposed surface, so as to favor the photocatalytic performance of titanium dioxide. A complete structural characterization was made by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. The remarkable photocatalytic performance together with the stability of the nano-system was demonstrated by degradation of the methylene blue dye in water. The non-toxicity of the nano-system was established by testing the effect of the material on the reproductive cycle of Mytilus galloprovincialis in an aquatic environment. The originally synthesized material was also compared to conventional TiO2 with Au nanoparticles on top. The latter system showed a dispersion of Au nanoparticles in the liquid environment, due to their instability in the aqueous solution that clearly represents an environmental contamination issue. Thus, the results show that nanometric TiO2 wrapping of Au nanoparticles has great potential in eco-friendly water/wastewater purification.