Study of Molecular-Level Dispersion of Pristine Graphene in Aqueous Media via Polyvinyl Alcohol Coil Physisorption.

Graphene has been widely used as a nanofiller in advanced electronic devices and nanocomposite materials to achieve enhanced electronic, mechanical, and barrier properties. Adequate polymers play the role of the composite matrix and can assist in the liquid-phase exfoliation of pristine graphene without any heavy chemical modification and the detriment of the properties of graphene. This stabilization mechanism is generally attributed to the steric forces formed between the polymer-adsorbed adsorbent. However, the key influence of the polymer concentration on the maximum graphene content in the colloidal solutions is still unclear. In this study, three different molar weights of water-soluble polyvinyl alcohol (PVA) were used for graphene dispersion. The influence of the PVA concentration on the graphene dispersion was systematically studied. Based on Flory's theory, we first proposed a model to describe the polymer adsorption process in the graphene/PVA/water ternary system in the "dilute" regime and simulated the adsorption-free energy changes during this transformation. This model is in good agreement with the experimental results and explains the critical polymer concentration, Cc, allowing the optimization of the graphene/polymer ratio. This fundamental understanding of polymer physisorption on 2D materials provides a simple method for producing nanocomposites with controlled nanosheet/polymer ratios and structures, which are of great interest for energy devices and biomaterials.

Foam Silica Films Synthesized by Calcium Chloride-Assisted Emulsification.

The development of porous films with an accessible high specific surface area is important for designing new adsorbents, sensors, or catalyst supports. Here, we describe a simple method to prepare a silica foam coating using a calcium chloride-assisted evaporation-induced emulsification method. An alcoholic silica sol containing calcium chloride and a poly(ethylene oxide)-based polymer is deposited on a substrate by dipping. The evaporation of the alcohol induces a phase separation between the silica-rich phase and the calcium-rich one. The size of the droplets increases via a coalescence process until the gelation of the sol, which determines the final pore size between 100 nm and 3 µm. Thermal analysis and monitoring of droplet evaporation confirm that the departure of the solvent is delayed by the presence of calcium chloride in the sol. The influence of the nature of the polymer on the porosity is discussed. The use of a block copolymer such as the Pluronic F-127, which strongly stabilizes the emulsion, allows to reach a low pore size (400 nm), while on the contrary, we propose to use a short poly(ethylene glycol) (PEG) such as PEG-400, which weakly stabilizes it, leading to larger pores (2-3 µm). Furthermore, we show that the addition of a zirconium salt (ZrOCl2·8H2O) to the silica sol accelerates the condensation step of the silica and leads to the decrease in the pore size.

Electrospinning of in situ synthesized silica-based and calcium phosphate bioceramics for applications in bone tissue engineering: A review.

The field of bone tissue engineering (BTE) focuses on the repair of bone defects that are too large to be restored by the natural healing process. To that purpose, synthetic materials mimicking the natural bone extracellular matrix (ECM) are widely studied and many combinations of compositions and architectures are possible. In particular, the electrospinning process can reproduce the fibrillar structure of bone ECM by stretching a viscoelastic solution under an electrical field. With this method, nano/micrometer-sized fibres can be produced, with an adjustable chemical composition. Therefore, by shaping bioactive ceramics such as silica, bioactive glasses and calcium phosphates through electrospinning, promising properties for their use in BTE can be obtained. This review focuses on the in situ synthesis and simultaneous electrospinning of bioceramic-based fibres while the reasons for using each material are correlated with its bioactivity. Theoretical and practical considerations for the synthesis and electrospinning of these materials are developed. Finally, investigations into the in vitro and in vivo bioactivity of different systems using such inorganic fibres are exposed.

Improving Formation Conditions and Properties of hBN Nanosheets Through BaF2-assisted Polymer Derived Ceramics (PDCs) Technique.

Hexagonal boron nitrite (hBN) is an attractive material for many applications such as in electronics as a complement to graphene, in anti-oxidation coatings, light emitters, etc. However, the synthesis of high-quality hBN at cost-effective conditions is still a great challenge. Thus, this work reports on the synthesis of large-area and crystalline hBN nanosheets via the modified polymer derived ceramics (PDCs) process. The addition of both the BaF2 and Li3N, as melting-point reduction and crystallization agents, respectively, led to the production of hBN powders with excellent physicochemical properties at relatively low temperatures and atmospheric pressure conditions. For instance, XRD, Raman, and XPS data revealed improved crystallinity and quality at a decreased formation temperature of 1200 °C upon the addition of 5 wt% of BaF2. Moreover, morphological determination illustrated the formation of multi-layered nanocrystalline and well-defined shaped hBN powders with crystal sizes of 2.74-8.41 ± 0.71 µm in diameter. Despite the compromised thermal stability, as shown by the ease of oxidation at high temperatures, this work paves way for the production of large-scale and high-quality hBN crystals at a relatively low temperature and atmospheric pressure conditions.

Advanced synthesis of highly crystallized hexagonal boron nitride by coupling polymer-derived ceramics and spark plasma sintering processes-influence of the crystallization promoter and sintering temperature.

Hexagonal boron nitride nanosheets (BNNSs) are promising 2D materials due to their exceptional chemical and thermal stabilities together with their electrical insulation properties. A combined synthesis method involving the polymer-derived ceramics (PDCs) route and the spark plasma sintering (SPS) process is proposed, leading to well-crystallized and pure layered h-BN crystals, prone to be exfoliated into large BNNSs. Here we focus more specifically on the influence of two key parameters of the process to be optimized: the Li3N concentration (0-10 wt%) and the SPS temperature (1200 °C-1950 °C). The presence of Li3N, added as crystal promoter in the pre-ceramic powder, significantly improves the crystallinity level of the product, as evidenced by XRD, SEM and Raman spectrometry. SPS temperature strongly modifies the size of the resulting h-BN flakes. The influence of SPS temperature on both purity and crystallinity is studied using cathodoluminescence. h-BN flakes larger than 200 µm2 (average flake area) are obtained. Few-layered BNNSs are successfully isolated, through exfoliation process.

Chitosan coating as an antibacterial surface for biomedical applications.

BACKGROUND AND OBJECTIVES: A current public health issue is preventing post-surgical complications by designing antibacterial implants. To achieve this goal, in this study we evaluated the antibacterial activity of an animal-free chitosan grafted onto a titanium alloy. METHODS: Animal-free chitosan binding on the substrate was performed by covalent link via a two-step process using TriEthoxySilylPropyl Succinic Anhydride (TESPSA) as the coupling agent. All grafting steps were studied and validated by means of X-ray Photoelectron Spectroscopy (XPS), Time-of-Flight secondary ion mass spectrometry (ToF-SIMS) analyses and Dynamic-mode Secondary Ion Mass Spectrometry (DSIMS). The antibacterial activity against Escherichia coli and Staphylococcus aureus strains of the developed coating was assessed using the number of colony forming units (CFU). RESULTS: XPS showed a significant increase in the C and N atomic percentages assigned to the presence of chitosan. A thick layer of polymer deposit was detected by ToF-SIMS and the results obtained by DSIMS measurements are in agreement with ToF-SIMS and XPS analyses and confirms that the coating synthesis was a success. The developed coating was active against both gram negative and gram positive tested bacteria. CONCLUSION: The success of the chitosan immobilization was proven using the surface characterization techniques applied in this study. The coating was found to be effective against Escherichia coli and Staphylococcus aureus strains.

In vitro toxicity assessment of extracts derived from sol-gel coatings on polycarbonate intended to be used in food contact applications.

Polycarbonate is a widely used polymer in food contact applications all around the world. However, due to the potential release of Bisphenol A (BPA) during repeated washing cycles, its use becomes compromised as BPA is known for being an endocrine disruptor for rodents. In order to tackle this issue, sol-gel coatings based on organoalkoxysiloxane were developed on PC, to act as a physical barrier. To this end, two sol-gel systems based on tetraethylorthosilicate (TEOS), methyltriethoxysilane (MTES) and 3-glycidyloxypropyltriethoxysilane (GPTES), three common sol-gel precursors, were prepared. The coatings derived from the latter two systems were then studied with regards to their potential toxicity in vitro. Migration tests were performed in food simulants, and the maximal migration was obtained in ethanol 10% (v/v) for one system and in isooctane for the other one. In vitro genotoxicity was assessed with the Ames test (OECD 471) and the micronucleus assay (OECD 487), and no genotoxic effect was observed. Moreover, the estrogenic activity of the extracts was studied with a transcriptional activation assay using transient transfection in human cells; none of the extracts was found estrogenic. These negative in vitro results are highly promising for the future use of these new barrier coating formulations onto food contact materials.

Pure &crystallized 2D Boron Nitride sheets synthesized via a novel process coupling both PDCs and SPS methods.

Within the context of emergent researches linked to graphene, it is well known that h-BN nanosheets (BNNSs), also referred as 2D BN, are considered as the best candidate for replacing SiO2 as dielectric support or capping layers for graphene. As a consequence, the development of a novel alternative source for highly crystallized h-BN crystals, suitable for a further exfoliation, is a prime scientific issue. This paper proposes a promising approach to synthesize pure and well-crystallized h-BN flakes, which can be easily exfoliated into BNNSs. This new accessible production process represents a relevant alternative source of supply in response to the increasing need of high quality BNNSs. The synthesis strategy to prepare pure h-BN is based on a unique combination of the Polymer Derived Ceramics (PDCs) route with the Spark Plasma Sintering (SPS) process. Through a multi-scale chemical and structural investigation, it is clearly shown that obtained flakes are large (up to 30 µm), defect-free and well crystallized, which are key-characteristics for a subsequent exfoliation into relevant BNNSs.

Atomically Sharp Interface in an h-BN-epitaxial graphene van der Waals Heterostructure.

Stacking various two-dimensional atomic crystals is a feasible approach to creating unique multilayered van der Waals heterostructures with tailored properties. Herein for the first time, we present a controlled preparation of large-area h-BN/graphene heterostructures via a simple chemical deposition of h-BN layers on epitaxial graphene/SiC(0001). Van der Waals forces, which are responsible for the cohesion of the multilayer system, give rise to an abrupt interface without interdiffusion between graphene and h-BN, as shown by X-ray Photoemission Spectroscopy (XPS) and direct observation using scanning and High-Resolution Transmission Electron Microscopy (STEM/HRTEM). The electronic properties of graphene, such as the Dirac cone, remain intact and no significant charge transfer i.e. doping, is observed. These results are supported by Density Functional Theory (DFT) calculations. We demonstrate that the h-BN capped graphene allows the fabrication of vdW heterostructures without altering the electronic properties of graphene.

In vitro genotoxicity assessment of MTES, GPTES and TEOS, three precursors intended for use in food contact coatings.

Organoalkoxysilanes are precursors that are used increasingly in the synthesis of food contact coatings. To comply with the EU regulation, their potential toxicity must be assessed, and very little information is known. The genotoxicity of three common precursors was studied, namely, tetraethylorthosilicate (TEOS), methyltriethoxysilane (MTES) and 3-glycidyloxypropyltriethoxysilane (GPTES). By the Ames test, MTES and TEOS were not mutagenic for bacteria. A significant positive response was observed with GPTES in the TA100 and TA1535 strains. The mutagenic effect was more pronounced in the presence of the exogenous metabolic activation system with an increase of the induction factor (ten-fold higher for the TA1535 strain). In the micronucleus assay performed with a human hepatoma cell line (HepG2 cells), GPTES gave negative results even in the presence of an exogenous activation system. To ascertain the possibility of using this precursor in food contact material, its migration must be monitored according to the coating formulation because migration might result in hazardous human exposure.

Independent control of adhesive and bulk properties of hybrid silica coatings on polycarbonate.

Transparent polymers are widely used in many applications ranging from automotive windows to microelectronics packaging. However, their intrinsic characteristics, in particular their mechanical properties, are significantly degraded with exposure to different weather conditions. For instance, under humid environment or UV-irradiation, polycarbonate (PC) undergoes depolymerization, leading to the release of Bisphenol A, a molecule presumed to be a hormonal disruptor, potentially causing health problems. This is a serious concern and the new REACH (Registration, Evaluation, Authorization and Restriction of Chemical substances ) program dictates that materials releasing Bisphenol A should be removed from the market by January 1st, 2015 (2012-1442 law). Manufacturers have tried to satisfy this new regulation by depositing atop the PC a dense oxide-like protective coating that would act as a barrier layer. While high hardness, modulus, and density can be achieved by this approach, these coatings suffer from poor adhesion to the PC as evidenced by the numerous delamination events occurring under low scratch constraints. Here, we show that the combination of a N2/H2-plasma treatment of PC before depositing a hybrid organic-inorganic solution leads to a coating displaying elevated hardness, modulus, and density, along with a very high adherence to PC (> 20 J/m(2) as measured by double cantilever beam test). In this study, the sol-gel coatings were composed of hybrid O/I silica (based on organoalkoxysilanes and colloidal silica) and designed to favor covalent bonding between the hybrid network and the surface treated PC, hence increasing the contribution of the plastic deformation from the substrate. Interestingly, double-cantilever beam (DCB) tests showed that the coating's adhesion to PC was the same irrespective of the organoalkoxysilanes/colloidal silica ratio. The versatility of the sol-gel deposition techniques (dip-coating, spray-coating, etc.), together with the excellent mechanical properties and exceptional adherence of this hybrid material to PC should lead to interesting new applications in diverse fields: optical eye-glasses, medical materials, packaging, and so forth.

Functionalization of titanium with chitosan via silanation: evaluation of biological and mechanical performances.

Complications in dentistry and orthopaedic surgery are mainly induced by peri-implant bacterial infections and current implant devices do not prevent such infections. The coating of antibacterial molecules such as chitosan on its surface would give the implant bioactive properties. The major challenge of this type of coating is the attachment of chitosan to a metal substrate. In this study, we propose to investigate the functionalization of titanium with chitosan via a silanation. Firstly, the surface chemistry and mechanical properties of such coating were evaluated. We also verified if the coated chitosan retained its biocompatibility with the peri-implant cells, as well as its antibacterial properties. FTIR and Tof-SIMS analyses confirmed the presence of chitosan on the titanium surface. This coating showed great scratch resistance and was strongly adhesive to the substrate. These mechanical properties were consistent with an implantology application. The Chitosan-coated surfaces showed strong inhibition of Actinomyces naeslundii growth; they nonetheless showed a non significant inhibition against Porphyromonas gingivalis after 32 hours in liquid media. The chitosan-coating also demonstrated good biocompatibility to NIH3T3 fibroblasts. Thus this method of covalent coating provides a biocompatible material with improved bioactive properties. These results proved that covalent coating of chitosan has significant potential in biomedical device implantation.

Synthesis of polystyrene coated SiC nanowires as fillers in a polyurethane matrix for electromechanical conversion.

Grafting of polystyrene (PS) from silica coating of silicon carbide nanowires (SiCNWs) has been performed by a two-step nitroxide mediated free radical polymerization (NMP) of styrene. First, an alkoxyamine based on N-tert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl) nitroxide (DEPN) was covalently attached onto NWs through free surface silanol groups. To immobilize the alkoxyamine initiator on the silica surface, alkoxylamine was formed in situ by the simultaneous reaction of polymerizable acryloxy propyl trimethoxysilane (APTMS), azobis isobutyronitrile (AIBN), and DEPN, which was used as a radical trap. Polystyrene chains with controlled molecular weights and narrow polydispersity were then grown from the alkoxyamine-functionalized NWs surface in the presence of a 'free' sacrificial styrylDEPN alkoxyamine. Both the initiator and polystyrene chains were characterized by FTIR and (13)C solid-state NMR and quantified by TGA. Ensuing nanocomposites were characterized by FEG-SEM, TEM and Raman spectroscopy. EDX analysis performed on functionalized nanowires during FEG-SEM analysis also gave evidence of grafting by a strong increase in the average C/Si atomic ratio. Incorporation of 2 wt% NWs into the polyurethane (PU) matrix has been carried out to prepare homogeneous nanocomposite films. The electric field induced thickness strain response has been investigated for the polystyrene-grafted silica coated SiC NWs (PU-SiC@SiO(2)@PS) nanocomposites and compared to pure polyurethane film and PU-SiC@SiO(2) nanocomposite without polystyrene grafting. At a moderate electric field of 10 V microm(-1), SiC@SiO(2)@PS loading increased the strain level of pure PU by a factor of 2.2. This improvement came partially due to polystyrene grafting since PU-SiC@SiO(2) films showed only a 1.7 times increase. The observed higher strain response of these nanocomposites makes them very attractive for micro-electromechanical applications.

Preparation of a mesoporous silicon boron nitride via a non-aqueous sol-gel route.

A silicon boron imide based gel Si3B(NH)x(NH2)y(NMe2)z was prepared via catalytic ammonolysis of tris[tris(dimethylamino)silylamino]boron B[HNSi[N(CH3)2]3]3; pyrolysis of the gel under ammonia at 1,000 degrees C gives a mesoporous silicon boron nitride with high surface area and narrow pore size distribution.