Unlocking the Potential of Liquid Plasma Polymer Films: Characterizing Aging Effects and Their Impact on the Wrinkling Phenomenon.

Here, we present the study of the intricate dynamics between the physicochemical properties of liquid propanethiol plasma polymer films (PPFs) and the formation of wrinkles in PPF/Al bilayers. The study investigates the effect of liquid PPF aging in the air before top Al layer deposition by magnetron sputtering on the wrinkling phenomenon for 4 days. Thanks to atomic force microscopy, the wrinkle dimensions were found to decrease by approximately 55% in amplitude and 66% in wavelength, correlated with an increase in the viscosity of the PPF over the aging duration (i.

Tailoring Oxygen Reduction Reaction Kinetics of Fe-N-C Catalyst via Spin Manipulation for Efficient Zinc-Air Batteries.

The interaction between oxygen species and metal sites of various orbitals exhibits intimate correlation with the oxygen reduction reaction (ORR) kinetics. Herein, a new approach for boosting the inherent ORR activity of atomically dispersed Fe-N-C matrix is represented by implanting Fe atomic clusters nearby. The as-prepared catalyst delivers excellent ORR activity with half-wave potentials of 0.

Designing Nanostructured Organic-Based Material by Combining Plasma Polymerization and the Wrinkling Approach.

In this work, an innovative and versatile strategy for the fabrication of nanostructured organic thin films is established based on the wrinkling phenomenon taking place in a bilayer system constituted by a liquid plasma polymer film (PPF) and a top Al coating. By means of morphological characterization (i.e.

Combining physical vapor deposition structuration with dealloying for the creation of a highly efficient SERS platform.

Nanostructured noble metal thin films are highly studied for their interesting plasmonic properties. The latter can be effectively used for the detection of small and highly diluted molecules by the surface-enhanced Raman scattering (SERS) effect. Regardless of impressive detection limits achieved, synthesis complexity and the high cost of gold restrict its use in devices.

Innovative One-Shot Paradigm to Tune Filler-Polymer Matrix Interface Properties by Plasma Polymer Coating in Osteosynthesis Applications.

The present study aims to improve the interfacial bonding between hydroxyapatite particles (HAs) and polylactide (PLA) to enhance the mechanical performance and biocompatibility of bone implants based on HA/PLA. For this, one-shot surface functionalization of HA via plasma polymerization is developed. Taking advantage of acetylene plasma chemistry, the hydrophobicity of HA particles was finely tuned prior to their introduction into a PLA matrix via an extrusion process.

Enhanced plasmonic processes in amino-rich plasma polymer films for applications at the biointerface.

A new plasmonic biosensor was developed in a planar chip-based format by coupling the plasmonic properties of gold nanoparticles (Au NPs) with the mechanical and bioadhesive features of unconventional organic thin films deposited from plasma, namely primary amine-based plasma polymer films (PPFs). A self-assembled layer of spherical Au NPs, 12 nm in diameter, was electrostatically immobilized onto optically transparent silanised glass. In the next step, the Au NP layer was coated with an 18 nm polymeric thick PPF layer the simultaneous polymerization/deposition of a cyclopropylamine (CPA) precursor performed by radio frequency discharge, both in pulsed and in continuous wave modes.

Investigating the relationship between the mechanical properties of plasma polymer-like thin films and their glass transition temperature.

This work aims at understanding the influence of the substrate temperature () on the viscoelastic properties of propanethiol plasma polymer films (PPFs). By means of state-of-the-art AFM characterization-based techniques including peak force quantitative nanomechanical mapping (PFQNM), nano dynamic mechanical analysis (nDMA) and "scratch" experiments, it has been demonstrated that the mechanical behaviour of PPFs is dramatically affected by the thermal conditions of the substrate. Indeed, the material behaves from a high viscous liquid ( viscosity ∼ 10 Pa s) to a viscoelastic solid (loss modulus ∼ 1.

Recent Advances in the Development of Nano-Sculpted Films by Magnetron Sputtering for Energy-Related Applications.

In this paper, we overview the recent progress we made in the magnetron sputtering-based developments of nano-sculpted thin films intended for energy-related applications such as energy conversion. This paper summarizes our recent experimental work often supported by simulation and theoretical results. Specifically, the development of a new generation of nano-sculpted photo-anodes based on TiO for application in dye-sensitized solar cells is discussed.

N-Doped TiO Photocatalyst Coatings Synthesized by a Cold Atmospheric Plasma.

This work presents a simple, fast (20 min treatment), inexpensive, and highly efficient method for synthesizing nitrogen-doped titanium dioxide (N-TiO) as an enhanced visible light photocatalyst. In this study, N-TiO coatings were fabricated by atmospheric pressure dielectric barrier discharge (DBD) at room temperature. The composition and the chemical bonds of the TiO and N-TiO coatings were characterized by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (ToF-SIMS).

Near interface ionic transport in oxygen vacancy stabilized cubic zirconium oxide thin films.

The cubic phase of pure zirconia (ZrO) is stabilized in dense thin films through a controlled introduction of oxygen vacancies (O defects) by cold-plasma-based sputtering deposition. Here, we show that the cubic crystals present at the film/substrate interface near-region exhibit fast ionic transport, which is superior to what is obtained with similar yttrium-stabilized cubic zirconia thin films.

Surface Engineering of Bromine-Based Plasma Polymer Films: A Step toward High Thiol Density Containing Organic Coatings.

Nowadays, the development of synthetic methods regarding the fabrication of -SH containing organic coatings continues to attract a considerable attention. Among the potential techniques, the plasma polymerization appears as one of the most promising method but the difficulty to control the chemical composition of the layers is highly limiting. In this context, in this work, we report on an original method combining dry and wet chemistry approaches in view of selectively incorporating -SH functions in organic coatings.

Fluorination of vertically aligned carbon nanotubes: from CF plasma chemistry to surface functionalization.

The surface chemistry of plasma fluorinated vertically aligned carbon nanotubes (vCNT) is correlated to the CF plasma chemical composition. The results obtained via FTIR and mass spectrometry are combined with the XPS and Raman analysis of the sample surface showing the dependence on different plasma parameters (power, time and distance from the plasma region) on the resulting fluorination. Photoemission and absorption spectroscopies are used to investigate the evolution of the electronic properties as a function of the fluorine content at the vCNT surface.

Spectroscopic observation of oxygen dissociation on nitrogen-doped graphene.

Carbon nanomaterials' reactivity towards oxygen is very poor, limiting their potential applications. However, nitrogen doping is an established way to introduce active sites that facilitate interaction with gases. This boosts the materials' reactivity for bio-/gas sensing and enhances their catalytic performance for the oxygen reduction reaction.

Surface tailoring of polyacrylate-grafted graphene oxide for controlled interactions at the biointerface.

The actual surface termination and lateral size of a nanomaterial is crucial in its interaction with biomolecules at the aqueous interface. Graphene oxide (GO) nanosheets have been demonstrated as promising nanoplatform for both diagnostic and therapeutic applications. To this respect, 'smart' GO nanocarriers have been obtained by the surface functionalisation with polymers sensitive, e.

Controlling the Formation of Nanocavities in Kirkendall Nanoobjects through Sequential Thermal Ex Situ Oxidation and In Situ Reduction Reactions.

Controlling the porosity, the shape, and the morphology of Kirkendall hollow nanostructures is the key factor to tune the properties of these tailor-made nanomaterials which allow in turn broadening their applications. It is shown that by applying a continuous oxidation to copper nanowires following a temperature ramp protocol, one can synthesize cuprous oxide nanotubes containing periodic copper nanoparticles. A further oxidation of such nanoobjects allows obtaining cupric oxide nanotubes with a bamboo-like structure.

Free-Radical-Induced Grafting from Plasma Polymer Surfaces.

With the advances in science and engineering in the second part of the 20th century, emerging plasma-based technologies continuously find increasing applications in the domain of polymer chemistry, among others. Plasma technologies are predominantly used in two different ways: for the treatment of polymer substrates by a reactive or inert gas aiming at a specific surface functionalization or for the synthesis of a plasma polymer with a unique set of properties from an organic or mixed organic-inorganic precursor. Plasma polymer films (PPFs), often deposited by plasma-enhanced chemical vapor deposition (PECVD), currently attract a great deal of attention.

Plasma fluorination of vertically aligned carbon nanotubes: functionalization and thermal stability.

Grafting of fluorine species on carbon nanostructures has attracted interest due to the effective modification of physical and chemical properties of the starting materials. Various techniques have been employed to achieve a controlled fluorination yield; however, the effect of contaminants is rarely discussed, although they are often present. In the present work, the fluorination of vertically aligned multiwalled carbon nanotubes was performed using plasma treatment in a magnetron sputtering chamber with fluorine diluted in an argon atmosphere with an Ar/F2 ratio of 95:5.

Towards higher stability of resonant absorption measurements in pulsed plasmas.

Possible ways to increase the reliability of time-resolved particle density measurements in pulsed gaseous discharges using resonant absorption spectroscopy are proposed. A special synchronization, called "dynamic source triggering," between a gated detector and two pulsed discharges, one representing the discharge of interest and another being used as a reference source, is developed. An internal digital delay generator in the intensified charge coupled device camera, used at the same time as a detector, is utilized for this purpose.

Simple method for gas temperature determination in CO₂-containing discharges.

A simple gas temperature determination method based on the line ratio between two rotational peaks from the CO Angstrom rotational emission band is reported. A formula based on CO spectral synthesis provides a way for temperature control in plasmas containing CO molecules. This approach is validated in a CO2 flowing gas surfaguide microwave discharge operating at 2.

Gas sensing with gold-decorated vertically aligned carbon nanotubes.

Vertically aligned carbon nanotubes of different lengths (150, 300, 500 µm) synthesized by thermal chemical vapor deposition and decorated with gold nanoparticles were investigated as gas sensitive materials for detecting nitrogen dioxide (NO2) at room temperature. Gold nanoparticles of about 6 nm in diameter were sputtered on the top surface of the carbon nanotube forests to enhance the sensitivity to the pollutant gas. We showed that the sensing response to nitrogen dioxide depends on the nanotube length.

Free radical generation and concentration in a plasma polymer: the effect of aromaticity.

Plasma polymer films (PPF) have increasing applications in many fields due to the unique combination of properties of this class of materials. Among notable features arising from the specifics of plasma polymerization synthesis, a high surface reactivity can be advantageously used when exploited carefully. It is related to the presence of free radicals generated during the deposition process through manifold molecular bond scissions in the energetic plasma environment.

Electron beam nanosculpting of Kirkendall oxide nanochannels.

The nanomanipulation of metal nanoparticles inside oxide nanotubes, synthesized by means of the Kirkendall effect, is demonstrated. In this strategy, a focused electron beam, extracted from a transmission electron microscope source, is used to site-selectively heat the oxide material in order to generate and steer a metal ion diffusion flux inside the nanochannels. The metal ion flux generated inside the tube is a consequence of the reduction of the oxide phase occurring upon exposure to the e-beam.

Modification of the adhesive properties of silicone-based coatings by block copolymers.

The improvement of the (bio)adhesive properties of elastomeric polydimethylsiloxane (PDMS) coatings is reported. This is achieved by a surface modification consisting of the incorporation of block copolymers containing a PDMS block and a poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) block in a PDMS matrix, followed by matrix cross-linking and immersion of the obtained materials in water. Contact angle measurements (CA), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) showed the presence of the PDMAEMA block at the surface, drastic morphology changes, and improved adhesion properties after immersion in water.

Use of free radicals on the surface of plasma polymer for the initiation of a polymerization reaction.

A novel approach to functionalize plasma polymer films (PPFs) through the grafting polymerization initiated from free radicals trapped in the film was developed in this work. 2-Ethylhexyl acrylate (EHA) was chosen as radically polymerizable monomer given the wide use of its corresponding polymer in coating and adhesive applications. The occurrence of the grafting was first confirmed by time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS).

Establishment of a derivatization method to quantify thiol function in sulfur-containing plasma polymer films.

Thiol-supported surfaces draw more and more interest in numerous fields of applications from biotechnology to catalysis. Among the various strategies to generate such surfaces, the plasma polymerization of a thiol-containing molecule appears to be one of the ideal candidates. Nevertheless, considering such an approach, a careful characterization of the material surface chemistry is necessary.