Iron oxide/graphene oxide nanocomposite synthesis using atmospheric cold plasma.

Herein, we demonstrate the use of an atmospheric pressure plasma with a Dielectric Barrier Discharge (DBD) for the synthesis of FeOx nanoparticles with a simultaneous formation of graphene oxide domains at low substrate temperature. For that, the interaction of the plasma to control good decomposition of the Fe precursor is essential and this is demonstrated by FTIR analyses. Thanks to a fine tuning of the plasma conditions, a homogeneous spatial distribution around 5 nm nanoparticles (NPs) was obtained, whereas without plasma, in the same configuration of the process, a heterogeneity regarding size and shape for the NPs was obtained. The Raman spectrum of the plasma deposit confirmed the presence of graphene oxide as the characteristic G and D bands were observed with I(D)/I(G) = 0.92. Thanks to optical emission spectroscopy (OES) measurements, it is proposed that the carbon deposition on FeOx nanoparticles is produced on the near plasma post discharge. XPS studies showed that the main contribution of iron was in Fe2+ form, corresponding to the FeO phase. No metallic Fe or carbide were detected. As there are many studies reporting the synergetic effect of FeOx NPs and graphene oxide, we believe that this new one-step simultaneous synthesis method may be of high interest for applications requiring direct deposition on temperature labile substrates such as polymers.

Gold nanoparticles synthesis and immobilization by atmospheric pressure DBD plasma torch method.

Herein, we report the impact of plasma on gold nanoparticles synthesis. We used an atmospheric plasma torch fed with an aerosolized tetrachloroauric(iii) acid trihydrate (HAuCl4·3H2O) solution. The investigation showed that using pure ethanol as a solvent for the gold precursor enabled a better dispersion compared to a water-containing solution. We demonstrated here that the deposition parameters are easy to control, presenting the influence of solvent concentration and deposition time. The advantage of our method is that no capping agent was used. We assume that plasma creates a carbon-based matrix around the gold nanoparticles preventing them to agglomerate. The XPS results revealed the impact of using plasma. Metallic gold was detected in the plasma-treated sample, whereas the no-plasma sample revealed only Au(i) and Au(iii) contributions originating from the HAuCl4 precursor. Detailed HRTEM, EDS mapping, and SAED analyses led to more insights into the structure.

Low Temperature Open-Air Plasma Deposition of SrTiO3 Films for Solar Energy Harvesting: Impact of Precursors on the Properties and Performances.

Strontium titanate (STO) is a well-known oxide used in a wide variety of applications due to its excellent stability and optoelectronic properties. However, its integration in photoelectrocatalytic devices is limited by the lack of fast and scalable methods to produce robust films at a low temperature and atmospheric pressure. Herein, we report an atmospheric pressure plasma-enhanced chemical vapor deposition (AP-PECVD) approach for the synthesis of STO crystalline films and their applications for photoelectrochemical solar energy conversion. The film crystallinity, which plays a determinant role in the photoelectrochemical performance, was linked to the selected strontium precursor and injection method. Through thermal stability studies of the precursors [Sr(dpm), Sr(ipo), Sr(acac), and Ti(ipo)] and analysis of the solution droplet size, it was demonstrated that the closer thermal decomposition behavior and superior miscibility of the Sr(dpm) and Ti(ipo) precursors led to more homogeneous and crystalline films with the highest photoelectrochemical performance (16.5 µA cm-2 at 1.23 V vs RHE under 100 mW cm-2), which can be further improved by a factor of 3.4 using thermal annealing at 500 °C. Evidence of the impact of a strontium precursor on the properties of STO films is provided through thermogravimetric analysis, X-ray diffraction, energy-dispersive system, UV-vis, X-ray photoelectron spectroscopy, HIM-SIMS, and photoelectrochemical analysis.

Atmospheric Aerosol Assisted Pulsed Plasma Polymerization: An Environmentally Friendly Technique for Tunable Catechol-Bearing Thin Films.

In this work, an atmospheric aerosol assisted pulsed plasma process is reported as an environmentally friendly technique for the preparation of tunable catechol-bearing thin films under solvent and catalyst free conditions. The approach relies on the direct injection of dopamine acrylamide dissolved in 2-hydroxyethylmethacrylate as comonomer into the plasma zone. By adjusting the pulsing of the electrical discharge, the reactive plasma process can be alternatively switch ON (tON) and OFF (tOFF) during different periods of time, thus allowing a facile and fine tuning of the catechol density, morphology and deposition rate of the coating. An optimal tON/tOFF ratio is established, that permits maximizing the catechol content in the deposited film. Finally, a diagram, based on the average energy input into the process, is proposed allowing for easy custom synthesis of layers with specific chemical and physical properties, thus highlighting the utility of the developed dry plasma route.

Anti-biofouling activity of Ranaspumin-2 bio-surfactant immobilized on catechol-functional PMMA thin layers prepared by atmospheric plasma deposition.

The deposition of polymeric thin layers bearing reactive functional groups is a promising solution to provide functionality on otherwise inert surfaces, for instance, for bioconjugation purposes. Atmospheric pressure plasma (AP plasma) deposition technology offers many advantages, such as fast deposition rates, low costs, low waste generation and suitability for coating various kind of material surfaces. In this work, the AP plasma-assisted copolymerization of methyl methacrylate (MMA) with a vinyl derivative of L-DOPA was studied in order to deposit coatings with reactive catechol/quinone groups suitable for protein covalent immobilization. The effect of adding a chemical cross-linker, between 0 and 2 mol%, to the monomer mixture is also studied in order to prepare robust plasma PMMA-based layers in liquid physiological media. The layer prepared with 0.2 mol% of cross-linker shows the best balance between stability in saline-buffered media and surface functionalization. Bioconjugation via the grafting of Ranaspumin-2 recombinant, a naturally occurring surfactant protein, is carried out in a single step after plasma deposition. Protein immobilization is corroborated by Quartz Crystal Microbalance with Dissipation (QCM-D) and Surface Plasmon Resonance (SPR) analyses and confirmed via Epicocconone staining, X-Ray Photoemission Spectroscopy (XPS) and Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) measurements and surface wettability characterizations. The bio-functionalized layers presented an enhanced activity against the adhesion of Human Serum Albumin (HSA), indicating the grafting potential of the Ranaspumin-2 bio-surfactant to produce anti-biofouling functional coatings.

Thermoresponsive Water-Soluble Polymer Layers and Water-Stable Copolymer Layers Synthesized by Atmospheric Plasma Initiated Chemical Vapor Deposition.

The growth of thermoresponsive layers with the atmospheric pressure plasma-initiated chemical vapor deposition (AP-PiCVD) process is reported for the first time. N-vinyl caprolactam (NVCL) was successfully homopolymerized and copolymerized with ethylene glycol dimethacrylate (EGDMA), yielding water-soluble and water-stable thermoresponsive thin films, respectively. Strong chemical retention and high thermoresponsivity were achieved, highlighting the ability of AP-PiCVD to grow functional conventional homopolymers and copolymers.

Precursors for Atmospheric Plasma-Enhanced Sintering: Low-Temperature Inkjet Printing of Conductive Copper.

Bidentate diamine and amino-alcohol ligands have been used to form solid, water-soluble, and air-stable monomeric copper complexes of the type [Cu(NH2CH2CH(R)Y)2(NO3)2] (1, R=H, Y=NH2; 2, R=H, Y=OH; 3, R=Me, Y=OH). The complexes were characterized by elemental analysis, mass spectrometry, infrared spectroscopy, thermal gravimetric analysis, and single-crystal X-ray diffraction. Irrespective of their decomposition temperature, precursors 1-3 yield highly conductive copper features [1.5×10-6â€…Ω m (±5×10-7â€…Ω m)] upon atmospheric-pressure plasma-enhanced sintering.

Transparent anti-fogging and self-cleaning TiO2/SiO2 thin films on polymer substrates using atmospheric plasma.

Transparent anti-fogging and self-cleaning coatings are of great interest for many applications, including solar panels, windshields and displays or lenses to be used in humid environments. In this paper, we report on the simultaneous synthesis, at atmospheric pressure, of anatase TiO2 nanoparticles and low-temperature, high-rate deposition of anatase TiO2/SiO2 nanocomposite coatings. These coatings exhibit durable super-hydrophilic and photocatalytic properties. The strategy followed relies on concomitant and separated injections of titania, i.e. titanium isopropoxide, and silica, i.e. hexamethyldisiloxane, precursors in the stream of a blown-arc discharge to form transparent anti-fogging and self-cleaning anatase TiO2/SiO2 nanocomposite coatings on polymer substrates.

Atmospheric Plasma Deposition of Methacrylate Layers Containing Catechol/Quinone Groups: An Alternative to Polydopamine Bioconjugation for Biomedical Applications.

Bioconjugation of enzymes on coatings based on polydopamine (PDA) layers is an appealing approach to control biological responses on biomedical implant surfaces. As alternative to PDA wet deposition, a fast, solvent-free, and dynamic deposition approach based on atmospheric-pressure plasma dielectric barrier discharge process is considered to deposit on metallic surfaces acrylic-based interlayers containing highly chemically reactive catechol/quinone groups. A biomimetic approach based on covalent immobilization of Dispersin B, an enzyme with antibiofilm properties, shows the bioconjugation potential of the novel plasma polymer layers. The excellent antibiofilm activity against Staphylococcus epidermidis is comparable to the PDA-based layers prepared by wet chemical methods with slow deposition rates. A study of preosteoblastic MG-63 human cell line viability and adhesion properties on plasma polymer layers demonstrates early interaction required for biomedical applications.

Anti-biofouling and antibacterial surfaces via a multicomponent coating deposited from an up-scalable atmospheric-pressure plasma-assisted CVD process.

Prevention of bacterial adhesion and biofilm formation on the surfaces of materials is a topic of major medical and societal importance. In this study, an up-scalable atmospheric-pressure plasma assisted deposition method is introduced to produce a multicomponent coating towards the elaboration of antibacterial and anti-biofilm surfaces. Interestingly, from a single catechol-based monomer, high deposition rates of highly chemically reactive functional thin films bearing catechol as well as quinone groups are achieved. The catechol-bearing thin film allows the in situ silver nanoparticle formation, assessed by scanning electron microscopy and EDX, whilst the enriched-quinone thin film is exploited for immobilizing dispersine B, an enzyme. In vitro functional assays demonstrated the dual antibacterial and anti-biofouling resistance properties of the coatings due to the antibacterial effect of silver and the fouling resistance of grafted dispersine B, respectively. Surfaces coated only with silver provide an antibacterial effect but fail to inhibit bacterial attachment, highlighting the usefulness of such dual-action surfaces. The approach presented here provides a simple and effective chemical pathway to construct powerful antibacterial surfaces for various industrial applications.

Significance of a Noble Metal Nanolayer on the UV and Visible Light Photocatalytic Activity of Anatase TiO2 Thin Films Grown from a Scalable PECVD/PVD Approach.

UV and visible light photocatalytic composite Pt and Au-TiO2 coatings have been deposited on silicon and glass substrates at low temperature using a hybrid ECWR-PECVD/MS-PVD process. Methylene blue, stearic acid, and sulfamethoxazole were used as dye, organic, and antibiotic model pollutants, respectively, to demonstrate the efficiency of these nanocomposite coatings for water decontamination or self-cleaning surfaces applications. Raman investigations revealed the formation of anatase polymorph of TiO2 in all synthesized coatings with a shifting of the main vibrational mode peak to higher wavenumber in the case of Au-TiO2 coating, indicating an increase number of crystalline defects within this coating. Because of the difference of the chemical potentials of each of the investigated noble metals, the sputtered metal layers exhibit different morphology. Pt sputtered atoms, with high surface adhesion, promote formation of a smooth 2D layer. On the other hand, Au sputtered atoms with higher cohesive forces promote the formation of 5-10 nm nanoparticles. As a result, the surface plasmon resonance phenomenon was observed in the Au-TiO2 coatings. UV photoactivity of the nanocomposite coatings was enhanced 1.5-3 times and 1.3 times for methylene blue and stearic acid, respectively, thanks to the enhancement of electron trapping in the noble metal layer. This electron trapping phenomenon is higher in the Pt-TiO2 coating because of its larger work function. On the other hand, the enhancement of the visible photoactivity was more pronounced (3 and 7 times for methylene blue and stearic acid, respectively) in the case of Au-TiO2 thanks to the surface plasmon resonance. Finally, these nanocomposite TiO2 coatings exhibited also a good ability for the degradation of antibiotics usually found in wastewater such as sulfamethoxazole. However, a complementary test have showed an increase of the toxicity of the liquid medium after photocatalysis, which could be due the presence of sulfamethoxazole's transformation byproducts.

Photocatalytic Anatase TiO2 Thin Films on Polymer Optical Fiber Using Atmospheric-Pressure Plasma.

Due to the undeniable industrial advantages of low-temperature atmospheric-pressure plasma processes, such as low cost, low temperature, easy implementation, and in-line process capabilities, they have become the most promising next-generation candidate system for replacing thermal chemical vapor deposition or wet chemical processes for the deposition of functional coatings. In the work detailed in this article, photocatalytic anatase TiO2 thin films were deposited at a low temperature on polymer optical fibers using an atmospheric-pressure plasma process. This method overcomes the challenge of forming crystalline transition metal oxide coatings on polymer substrates by using a dry and up-scalable method. The careful selection of the plasma source and the titanium precursor, i.e., titanium ethoxide with a short alkoxy group, allowed the deposition of well-adherent, dense, and crystalline TiO2 coatings at low substrate temperature. Raman and XRD investigations showed that the addition of oxygen to the precursor's carrier gas resulted in a further increase of the film's crystallinity. Furthermore, the films deposited in the presence of oxygen exhibited a better photocatalytic activity toward methylene blue degradation assumedly due to their higher amount of photoactive {101} facets.

Models for biomedical interfaces: a computational study of quinone-functionalized amorphous silica surface features.

A density functional theory (PBE functional) investigation is carried out, in which a model of an amorphous silica surface is functionalized by ortho-benzoquinone. Surface functionalization with catechol and quinone-based compounds is relevant in biomedical fields, from prosthetic implants to dentistry, to develop multifunctional coatings with antimicrobial properties. The present study provides atomistic information on the specific interactions between the functionalizing agent and the silanol groups at the silica surface. The distinct configurations of the functional groups, the hydrogen bond pattern, the role of dispersion forces and the simulated IR spectra provide detailed insight into the features of this model surface coating. Ab initio molecular dynamics gives further insights into the mobility of the functionalizing groups. As a final step, we studied the condensation reaction with allylamine, via Schiff base formation, to ground subsequent simulations on condensation with model peptides of antimicrobial activity.

Efficient Flame Retardant Thin Films Synthesized by Atmospheric Pressure PECVD through the High Co-deposition Rate of Hexamethyldisiloxane and Triethylphosphate on Polycarbonate and Polyamide-6 Substrates.

An innovative approach to produce high-performance and halogen-free flame-retardant thin films at atmospheric pressure is reported. PDMS-based coatings with embedded dopant-rich polyphosphates are elaborated thanks to a straightforward approach, using an atmospheric pressure dielectric barrier discharge (AP-DBD). Deposition conditions have been tailored to elaborate various thin films that can match the fire performance requirements. Morphology, chemical composition, and structure are investigated, and results show that the coatings performances are increased by taking advantage of the synergistic effect of P and Si flame retardant compounds. More specifically, this study relates the possibility to obtain flame retardant properties on PolyCarbonate and PolyAmide-6 thanks to their covering by a 5 µm thick coating, i.e. very thin films for this field of application, yet quite substantial for plasma processes. Hence, this approach enables deposition of flame retardant coatings onto different polymer substrates, providing a versatile fireproofing solution for different natures of polymer substrates. The presence of an expanded charred layer at the surface acts as a protective barrier limiting heat and mass transfer. This latter retains and consumes a part of the PC or PA-6 degradation byproducts and then minimizes the released flammable gases. It may also insulate the substrate from the flame and limit mass transfers of remaining volatile gases. Moreover, reactions in the condensed phase have also been highlighted despite the relatively thin thickness of the deposited layers. As a result of these phenomena, excellent performances are obtained, illustrated by a decrease of the peak of the heat release rate (pHRR) and an increase of the time to ignition (TTI).

Organo-Chlorinated Thin Films Deposited by Atmospheric Pressure Plasma-Enhanced Chemical Vapor Deposition for Adhesion Enhancement between Rubber and Zinc-Plated Steel Monofilaments.

A continuous-flow plasma process working at atmospheric pressure is developed to enhance the adhesion between a rubber compound and a zinc-plated steel monofilament, with the long-term objective to find a potential alternative to the electrolytic brass plating process, which is currently used in tire industry. For this purpose, a highly efficient tubular dielectric barrier discharge reactor is built to allow the continuous treatment of "endless" cylindrical substrates. The best treatment conditions found regarding adhesion are Ar/O2 plasma pretreatment, followed by the deposition from dichloromethane of a 75 nm-thick organo-chlorinated plasma polymerized thin film. Ar/O2 pretreatment allows the removal of organic residues, coming from drawing lubricants, and induces external growth of zinc oxide. The plasma layer has to be preferably deposited at low power to conserve sufficient hydrocarbon moieties. Surface analyses reveal the complex chemical mechanism behind the establishment of strong adhesion levels, more than five times higher after the plasma treatment. During the vulcanization step, superficial ZnO reacts with the chlorinated species of the thin film and is converted into porous and granular bump-shaped ZnwOxHyClz nanostructures. Together, rubber additives diffuse through the plasma layer and lead to the formation of zinc sulfide on the substrate surface. Hence, two distinct interfaces, rubber/thin film and thin film/substrate, are established. On the basis of these observations, hypotheses explaining the high bonding strength results are formulated.

Computational Study of Acidic and Basic Functionalized Crystalline Silica Surfaces as a Model for Biomaterial Interfaces.

In silico modeling of acidic (CH2COOH) or basic (CH2NH2) functionalized silica surfaces has been carried out by means of a density functional approach based on a gradient-corrected functional to provide insight into the characterization of experimentally functionalized surfaces via a plasma method. Hydroxylated surfaces of crystalline cristobalite (sporting 4.8 OH/nm(2)) mimic an amorphous silica interface as unsubstituted material. To functionalize the silica surface we transformed the surface Si-OH groups into Si-CH2COOH and Si-CH2NH2 moieties to represent acidic/basic chemical character for the substitution. Structures, energetics, electronic, and vibrational properties were computed and compared as a function of the increasing loading of the functional groups (from 1 to 4 per surface unit cell). Classical molecular dynamics simulations of selected cases have been performed through a Reax-FF reactive force field to assess the mobility of the surface added chains. Both DFT and force field calculations identify the CH2NH2 moderate surface loading (1 group per unit cell) as the most stable functionalization, at variance with the case of the CH2COOH group, where higher loadings are preferred (2 groups per unit cell). The vibrational fingerprints of the surface functionalities, which are the ν(C═O) stretching and δ(NH2) bending modes for acidic/basic cases, have been characterized as a function of substitution percentage in order to guide the assignment of the experimental data. The final results highlighted the different behavior of the two types of functionalization. On the one hand, the frequency associated with the ν(C═O) mode shifts to lower wavenumbers as a function of the H-bond strength between the surface functionalities (both COOH and SiOH groups), and on the other hand, the δ(NH2) frequency shift seems to be caused by a subtle balance between the H-bond donor and acceptor abilities of the NH2 moiety. Both sets of data are in general agreement with experimental measurements on the corresponding silica-functionalized materials and provide finer details for a deeper interpretation of experimental spectra.

Atmospheric pressure plasma-initiated chemical vapor deposition (AP-PiCVD) of poly(diethylallylphosphate) coating: a char-forming protective coating for cellulosic textile.

An innovative atmospheric pressure chemical vapor deposition method toward the deposition of polymeric layers has been developed. This latter involves the use of a nanopulsed plasma discharge to initiate the free-radical polymerization of an allyl monomer containing phosphorus (diethylallylphosphate, DEAP) at atmospheric pressure. The polymeric structure of the film is evidence by mass spectrometry. The method, highly suitable for the treatment of natural biopolymer substrate, has been carried out on cotton textile to perform the deposition of an efficient and conformal protective coating.

Dual application of (aqua)(chlorido)(porphyrinato)chromium(III) as hypersensitive amine-triggered ON switch and for dioxygen activation.

Although synthesis and substitution reactions of chlorido chromium(III) porphyrins Cr(III)(TPP)(Cl)(L) (H2TPP = 5,10,15,20-tetraphenyl porphyrin, L = pyridine, H2O, ROH, etc.), have been well-established in coordination chemistry for decades, an unexpected dichotomous reactivity of Cr(III)(TPP)(Cl)(H2O) (1) toward amines is disclosed here. This reactivity leads to the application of 1 as highly sensitive substoichiometric and irreversible ON switch for amine detection by an autocatalytic pathway. The concomitant activation of O2 by the 1/amine system is furthermore exploited in an electrochemically driven epoxidation of norbonene using O2 as initial oxidant.

Temperature-dependent wear mechanisms for magnetron-sputtered AlTiTaN hard coatings.

AlTiTaN coatings have been demonstrated to have high thermal stability at temperatures up to 900 °C. It has been speculated that the high oxidation resistance promotes an improved wear resistance, specifically for dry machining applications. This work reports on the influence of temperature up to 900 °C on the wear mechanisms of AlTiTaN hard coatings. DC magnetron-sputtered coatings were obtained from an Al(46)Ti(42)Ta(12) target, keeping the substrate bias at -100 V and the substrate temperature at 265 °C. The coatings exhibited a single-phase face-centered cubic AlTiTaN structure. The dry sliding tests revealed predominant abrasion and tribo-oxidation as wear mechanisms, depending on the wear debris formed. At room temperature, abrasion leading to surface polishing was observed. At 700 and 800 °C, slow tribo-oxidation and an amorphous oxide formed reduced the wear rate of the coating compared to room temperature. Further, an increase in temperature to 900 °C increased the wear rate significantly due to fast tribo-oxidation accompanied by grooving. The friction coefficient was found to decrease with temperature increasing from 700 to 900 °C due to the formation of oxide scales, which reduce adhesion of asperity contacts. A relationship between the oxidation and wear mechanisms was established using X-ray diffraction, Raman spectroscopy, scanning electron microscopy, surface profilometry, confocal microscopy, and dynamic secondary ion mass spectrometry.

Influence of temperature on oxidation mechanisms of fiber-textured AlTiTaN coatings.

The oxidation kinetics of AlTiTaN hard coatings deposited at 265 °C by DC magnetron sputtering were investigated between 700 and 950 °C for various durations. By combining dynamic secondary ion mass spectrometry (D-SIMS), X-ray diffraction (XRD), and transmission electron microscopy (TEM) investigations of the different oxidized coatings, we were able to highlight the oxidation mechanisms involved. The TEM cross-section observations combined with XRD analysis show that a single amorphous oxide layer comprising Ti, Al, and Ta formed at 700 °C. Above 750 °C, the oxide scale transforms into a bilayer oxide comprising an Al-rich upper oxide layer and a Ti/Ta-rich oxide layer at the interface with the coated nitride layer. From the D-SIMS analysis, it could be proposed that the oxidation mechanism was governed primarily by inward diffusion of O for temperatures of ≤700 °C, while at ≥750 °C, it is controlled by outward diffusion of Al and inward diffusion of O. Via a combination of structural and chemical analysis, it is possible to propose that crystallization of rutile lattice favors the outward diffusion of Al within the AlTiTa mixed oxide layer with an increase in the temperature of oxidation. The difference in the mechanisms of oxidation at 700 and 900 °C also influences the oxidation kinetics with respect to oxidation time. Formation of a protective alumina layer decreases the rate of oxidation at 900 °C for long durations of oxidation compared to 700 °C. Along with the oxidation behavior, the enhanced thermal stability of AlTiTaN compared to that of the TiAlN coating is illustrated.