Atmospheric Pressure Plasma Initiated Chemical Vapor Deposition Using Ultra‐Short Square Pulse Dielectric Barrier Discharge

Abstract

A simple, efficient and scalable method for the atmospheric pressure plasma initiated chemical vapor deposition of conventional polymer is demonstrated. Ultra‐short square pulse dielectric barrier discharge, which allows high deposition rates even for plasma duty cycle as low as 0.01%, is used to deposit a glycidyl methacrylate (GMA) polymer layer. The polymer structure of the thin films is evidenced by matrix‐assisted laser desorption/ionization high‐resolution mass spectrometry. Polymer molecular weights up to 30 000 g mol−1 are found by size exclusion chromatography (SEC), highlighting the suitability of the plasma initiated CVD method for the deposition of polymer layers.

Co‐Deposition of Plasma‐Polymerized Polyacrylic Acid and Silver Nanoparticles for the Production of Nanocomposite Coatings Using a Non‐Equilibrium Atmospheric Pressure Plasma Jet

“…[41] This result can be probably attributed to the low value of duty cycle employed for the co-deposition process: in fact, as highlighted by Boscher et al [55] in their work on the deposition of plasma-polymerized poly(glycidyl methacrylate) by means of DBD driven by ultra-short square pulses, the increase of the duty cycle leads to functional groups destruction and to the formation of a larger distribution of chemical bonds; conversely, films deposited using lower duty cycle conditions were found to be identical in terms of chemical composition to the ones obtained for conventionally polymerized poly(glycidyl methacrylate). [55] High-resolution XPS spectra of the Ag 3d are reported in Figure 8 and indicate that the binding energies of the corresponding spin orbit splitting of Ag 3d5/2 and Ag 3d3/2 due to AgNPs are centered at 368.2 eV and 374.2 eV, respectively. Nonetheless, the binding energy positions of Ag 3d were not enough to identify the oxidation state of the Ag species because the characteristic states of oxidized and metallic silver are close together.…”

Self‐Defensive Coating for Antibiotics Degradation—Atmospheric Pressure Chemical Vapor Deposition of Functional and Conformal Coatings for the Immobilization of Enzymes

“…The plasma-polymerized GMA thin fi lms were deposited in an atmospheric pressure dielectric barrier discharge (AP-DBD) reactor, as previously described. [ 26 ] The plasma set-up is made of two high voltage electrodes (18.72 cm 2 ) and a stainless steel moving table as ground electrode. An ultrashort square pulse AP-DBD, generated using an AHTPB10F generator from EFFITECH (Gif-sur-Yvette, France), and was used to ignite the plasma discharge.…”

“…[ 26 ] Prior to the CVD step, samples are cleaned with solvents (butanone/acetone/ ethanol) and just before deposition are exposed to a continuous 1 W cm −2 argon/oxygen plasma discharge (generated by a 10 kHz sinusoidal signal with a Softal generator) to remove remaining impurities and form surface hydroxyl, carbonyl, and carboxylic acid groups. [ 29,30 ] Those groups provide during the subsequent deposition step reactive radicals groups to ensure the covalent anchoring of the formed polymer coating to the surface material.…”

“…Indeed, the ultrashort homogeneous discharge generated at atmospheric pressure thanks to a fast voltage rise (i.e., tens of nanoseconds), conveniently replaced the initiator and heating fi laments used in iCVD by producing a range of reactive species with some of them that will efficiently initiate the free-radical polymerization reaction. [ 26 ] The well-reported negative impact of plasma on the monomer was minimized by pulsing the ultrashort plasma discharges (≈ t ON = 100 ns) at very low frequencies (≈100 to 1000 Hz). As a consequence, plasma only affects the chemistry of the fi lm for a very small portion of the time (≈0.003%), whereas the free-radical polymerization pathway reaction occurs solely during most of the plasma-off time ( t OFF = 33 ms) and polymer coatings with maximum functional groups retention are formed.…”

“…[ 27 ] In this work, epoxy functionalized coatings are synthesized by plasma polymerization of glycidyl methacrylate (GMA) via PiCVD at atmospheric pressure. [ 26 ] The coatings, deposited on various materials, are used for the grafting of two enzymes able to degrade antibiotics, i.e., laccase and β-lactamase. The infl uence of their covalent immobilization on sulfamethoxazole and amoxicillin degradation performances is studied.…”