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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.

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.

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.

In this paper, we report a new and easily up-scalable dry chemical method to functionalize with diene and dienophile groups a large range of surfaces, such as metal, polymer, or glass, and we demonstrate the potentiality of this technique to realize thermally responsive adhesion between these materials. A complete and extensive surface chemistry analysis of the grafted surfaces, based on the deposition of an anhydride-rich thin plasma polymer layer by using an atmospheric pressure dielectric barrier discharge (DBD) plasma process, and its subsequent gas phase aminolysis reaction with specific diene or dienophile compound is discussed. The optimization of the assembling condition for these tailored surfaces has led to achieve a Diels-Alder adhesion force up to 0.6 N/mm at ambient temperature, which can be reduced by a factor of 50 when the retro Diels-Alder is ignited at a heating temperature around 200 °C. The study of the failure interface produced after peeling tests is presented and a mechanism of failure is proposed, based on forensic analyses involving surface analytical techniques such as XPS, ToF-SIMS, and SEM combined to AFM analyses for the retrieving of chemical and morphological information.

In order to functionalize silicon carbide nanopowders with carboxylic groups, an r.f. (13.56 MHz) low pressure plasma reactor has been developed so that particles can be stirred during the processing to try to coat them on their whole surface. Coatings in an O 2 /hexamethyldisilazane (HMDSN) mixture have first been optimized on flat substrates; X-ray Photoelectron Spectroscopy (XPS) analysis showed that the O 2 /HMDSN gas mixture resulted in a coating evolving from a polymer-like structure to a more inorganic SiO x -like structure as the oxygen ratio increased. For a large O 2 /HMDSN value, carboxylic groups were detected on the sample surface. Silicon carbide nanoparticles have then been plasma processed in such a reactive atmosphere. XPS, Time of Flight Secondary Ion Mass Spectroscopy (ToF-SIMS) and Transmission Electron Microscopy (TEM) analyses evidenced the surface modification of the processed powder and confirmed the grafting of carboxylic groups.

A natural vulcanized rubber was treated by atmospheric dielectric barrier discharges to improve its adhesion to silicone adhesive. The different operating conditions were: (i) the nature of the plasma gas associated or not with organic precursors such as acetic acid or allyl alcohol, (ii) the concentration of the precursors in the gas phase, (iii) the power discharge (between 500 and 1 000 W) and (iv) the treatment time (between 18 and 30 s). The surface modifications induced by the plasma treatments were characterized by water contact angle measurements and XPS analyses. T-peel tests were carried out to evaluate the influence of the surface modifications on the adhesion properties of the treated rubber. The efficiency of plasma treatments with the use of allyl alcohol has been proved for the adhesion improvement of natural vulcanized rubbers to a silicone adhesive (increase by a factor of 10). XPS analysis revealed that this treatment induced an increase of the total oxygen amount in the sample with the preferential formation of CO bonds, which might explain the adhesion improvement observed.

Adhesion of epoxy resins on copper foils for printed circuit board (PCB) applications is improved by nearly a factor of 5, using surface cleaning and deposition of a 15-nm-thick film in a low-pressure remote plasma-enhanced chemical vapor deposition process. The cleaning pretreatment, using an N2–O2 oxidizing gas mixture with moderate heating (343 K), gives the best results. This pretreatment removes the carbonaceous contaminants present on the topmost surface of the sample and slightly oxidizes the copper into CuO. This oxide is then reduced during the deposition treatment, presumably by reaction with the aminopropyltrimethoxysilane (APTMS) precursor. The surface roughness is unchanged after treatment, thereby showing that the improvement of the copper/epoxy adhesion is only due to the chemistry of the plasma coating. Applying these results to dielectric barrier discharges allows us to achieve the same level of adhesion, which, therefore, does not depend on the process.