Soft plasma polymer coatings based on atomic polymerization (original) (raw)
Related papers
RSC Advances, 2012
Plasma polymer films produced via dielectric barrier discharge under atmospheric conditions can simultaneously host charged segments and poly(dimethysiloxane)/silica like polymers. The former segments afford some anion exchange properties and the latter ones allow stabilization of the whole coating in the presence of water. The anion exchange capacity of the film can then be used to nucleate and to grow inorganic particles in the plasma polymer coating. In particular, we exploit the presence of allylamine oligomers in a plasma coating made from a mixture of allylamine and hexamethyldisiloxane to hydrolyse titanium(IV) (bisammonium lactato dihydroxyde) and to condense it in TiO 2 . As a second example, Prussian Blue is produced by the successive incubation of the coating in a solution of potassium hexacyanoferrate and iron(III) chloride. The distribution of TiO 2 and of Prussian Blue across the film thickness is investigated, in a semi quantitative manner, by means of Rutherford backscattering. The functional properties of the hybrid coatings are then investigated and it is found that the TiO 2 containing films display photoinduced hydrophilicity whereas the films with Prussian Blue display magnetic properties. { Electronic Supplementary Information (ESI) available: Cross-sectional SEM analysis of a plasma polymer coating, Zeta potential titration of the glass wafer and of the glass wafer coated with a plasma polymer film made from an HMDMSO-Aam blend, SEM image of an inorganic cluster grown on the surface of a plasma polymer film deposited from a mixture of HMDMSO and Aam after exposure to a solution containing 5 mM of [Ti(IV)Lac 2 OH 2 ] 22 anions, SEM micrograph of a plasma polymer film made from a blend of HMDMSO and Aam and subsequently put in contact with 1 mM Fe(CN) 6 42 and 10 mM Fe 3+ containing solution, Fe2p region of the XPS spectrum of a HMDMSO-Aam plasma coating put in the successive presence of 1 mM potassium hexacyanoferaate and 10 mM iron(III) chloride, RBS spectra of a HMDMSO-Aam plasma coating after in situ formation of TiO 2 and BP. See
Crystalline and Non-crystalline Solids, 2016
Recently, many efforts have been done to chemically functionalize sensors surface to achieve selectivity towards diagnostics targets, such as DNA, RNA fragments and protein tumoural biomarkers, through the surface immobilization of the related specific receptor. Especially, some kind of sensors such as microcantilevers (gravimetric sensors) and one-dimensional photonics crystals (optical sensors) able to couple Bloch surface waves are very sensitive. Thus, any kind of surface modifications devoted to functionalize them has to be finely controlled in terms of mass and optical characteristics, such as refractive index, to minimize the perturbation, on the transduced signal, that can affect the response sensitivity towards the detected target species. In this work, the study and optimization of ultra-thin plasma polymers and copolymers, compatible with these constrains and obtained from the vapours of acrylic acid containing a carboxylic (−COOH) group and styrene (an aromatic molecule with a vinyl as substituent at the ring), are reported. The obtained plasma polyacrylic acid (PPAA), plasma polystyrene (PPST) and their copolymer (PPAA-ST), characterized through optical contact angle analysis (OCA), Fourier transform infrared (FTIR) spectroscopy in attenuated total reflection (ATR-FTIR), X-ray photoelectrons spectroscopy (XPS), and atomic force microscopy (AFM), are shown to match specific and critical requirements, such as low thickness (∼40 nm) and refractive index (∼1.5), high surface density of reactive groups (10 15-10 16 COOH/cm 2), bioantifouling properties where required, reproducibility, and chemical resistance and stability.
Plasma Polymerization: Electronics and Biomedical Application
Plasma Science and Technology for Emerging Economies, 2017
Polymer thin films have received great interest in recent past because of their wide range of physical, chemical, mechanical, electrical and biological properties, which make them well suited for innumerable applications in fields of mechanics, optics, and electronics [1-3]. Polymer thin films can be fabricated using a variety of methods. Based on the nature of the fabrication process, these methods can be broadly divided into two categories: "wet" solution-based processing, e.g., spin coating and dip coating, or "dry" methods, e.g., physical vapor deposition (PVD) and chemical vapor deposition (CVD). Plasma polymerization is a type of CVD used extensively to synthesize polymer thin films from organic and inorganic precursors, where plasma discharge is used to catalyze the chemical reactions leading to formation of the polymer structure [4, 5]. Hence, plasma polymers can be generally defined as thin films of material which are formed as a result of interaction of monomer (organic and inorganic) vapor in the plasma (glow) discharge [6]. Although the word polymer is used, this special class of material differs from conventional polymers in several respects. Most notably, plasma polymers generally lack regular repeating unit, their chains are often short, randomly branched, and highly cross-linked. As the result of their unique chemical structure, these polymers generally do not exhibit distinct glass transition temperatures and have high elastic moduli, excellent mechanical, thermal and chemical stability, and outstanding adhesion to a variety of substrates [5]. Their chemical composition and thickness can be easily controlled by controlling the deposition parameters and the nature of
Controlled wettability, same chemistry: biological activity of plasma-polymerized coatings
2012
Plasma polymerization was used to produce novel nanometric coatings able to direct fibronectin adsorption and cell response. Using ethyl acrylate as a monomer, we obtain coatings whose chemical composition maintains some of the characteristic functionalities of the photo-initiated polymer, while the water contact angle increases monotonically with the duration of the plasma discharge.
Plasma and Polymers: Recent Progress and Trends
Molecules
Plasma-enhanced synthesis and modification of polymers is a field that continues to expand and become increasingly more sophisticated. The highly reactive processing environments afforded by the inherently dynamic nature of plasma media are often superior to ambient or thermal environments, offering substantial advantages over other processing methods. The fluxes of energy and matter toward the surface enable rapid and efficient processing, whereas the charged nature of plasma-generated particles provides a means for their control. The range of materials that can be treated by plasmas is incredibly broad, spanning pure polymers, polymer-metal, polymer-wood, polymer-nanocarbon composites, and others. In this review, we briefly outline some of the recent examples of the state-of-the-art in the plasma-based polymer treatment and functionalization techniques.
Macromolecular Materials and Engineering, 2009
The process of plasma curing of functional acrylates has been studied. For these purposes, a nitrogen plasma generated by a flat and a cylindrical electrode configuration, respectively, was used to provide both planar and 3D curing conditions. In selected cases, a double bond conversion >95% was observed by ATR-IR spectroscopy for a 15 mm (wet thickness) acrylate coating even without the addition of any photoinitiator. Compared to UV curing, the surface energy of the cured substrates was significantly higher when plasma curing was applied (>70 mN Á m À1 ); however, the hydrophilic surfaces experienced hydrophobic recovery. Finally, the generation of microstructures on uniaxially oriented substrates during the plasma process was studied and conditions for their tailor-made creation are suggested.
Surface Functionalization of Polymers under Cold Plasma Conditions-A Mechanistic Approach
Journal of Photopolymer Science and Technology, 1997
Cold plasma conditions offer a novel route for synthesizing and depositing macromolecular structures on various organic and inorganic surfaces, and to functionalize in a controlled manner even the most inert polymeric substrates. The energies of active species of plasma are high enough to split all chemical bonds from organic and organometallic derivatives and consequently, tailored macromolecular structures can be created through controlled recombination of plasma generated charged and neutral molecular fragments. Nonmacromolecular forming active species of organic-or inorganic-origin can interact with polymeric surfaces creating desired, new thin layer structures through in situ or ex-situ recombination mechanisms initiated between the plasma generated active sites of the condensed and gaseous phases. Understanding the plasma induced reaction mechanisms developed in the gas phase and on the surfaces which limit the discharge opens up rational ways to create materials with advanced surface characteristics, such as chemical inertness, advanced hydrophobicity or hydrophilicity, selective reactivity (molecular recognition), intense surface roughness, etc.
Modification of surface properties of bell metal by radiofrequency plasma polymerization
Journal of Theoretical and Applied Physics, 2012
Radiofrequency (RF) plasma polymerization is a convenient thin film deposition process as it facilitates the synthesis of polymer films with stable physico-chemical properties suitable for various applications in microelectronic, optical, and biomedical fields. The unique properties of these plasma polymerized films as compared to the conventional ones are strongly related to the proper adjustment of the external plasma discharge parameters and selection of suitable monomer. It is also important to study the fundamental chemistry of RF plasma polymerization process, so that one can successfully correlate the internal features of the discharge with the film properties and explore their possible technological applications. The possibility of using styrene-based plasma polymer (SPP) films on bell metal as protective coatings is explored in this work. Depositions of the films are carried out in RF Ar/styrene discharge at working pressure of 1.2 × 10 −1 mbar and at the RF power range of 20 to 110 W. Optical emission spectroscopy (OES) is used to study the active species generated during plasma polymerization, while Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) are used to analyze the internal chemical structures of the films. The protective performances of the SPP films are attempted to correlate with the results obtained from OES, FT-IR, and XPS analyses.
ACS Nano, 2014
We report on the synthesis of hard, adhesive, and highly transparent bilayer organosilicate thin films on large poly(methyl methacrylate) substrates by atmospheric plasma, in ambient air, at room temperature, in a one-step process, using a single precursor. The method overcomes the challenge of fabricating coatings with high mechanical and interfacial properties in a one-step process. The bottom layer is a carbon-bridged hybrid silica with excellent adhesion with the poly(methyl methacrylate) substrate, and the top layer is a dense silica with high Young's modulus, hardness, and scratch resistance. The bilayer structure exhibited ∼100% transmittance in the visible wavelength range, twice the adhesion energy and three times the Young's modulus of commercial polysiloxane solÀgel coatings.
New Insights into the Substrate–Plasma Polymer Interface
The Journal of Physical Chemistry B, 2011
We describe a new method to characterize the underside (substrate interface) of plasma polymer (PP) thin films via their simple delamination from a sodium chloride single crystal substrate. By depositing the PP film onto an ionic bonded surface such as a sodium chloride crystal, the PP films investigated were easily delaminated from the substrate. Two plasma polymer films deposited from 1-bromopropane (BrPP) and allylamine (AAPP) were used to exemplify this new technique. The top- and underside (substrate–plasma polymer interface) of the films were examined by X-ray photoelectron spectroscopy (XPS) and synchrotron-based near edge X-ray adsorption fine structure (NEXAFS) spectroscopy. The results demonstrate that both films exhibit heterogeneous film structures with their chemical composition and levels of unsaturated species. The underside of both the BrPP and the AAPP films exhibited higher concentrations of oxygen, while their topsides contained higher levels of unsaturated species. These results provide useful insights into the BrPP and AAPP film formation and the chemistry. The delamination technique provides a simple method to analyze the early stages of film chemistry for plasma polymer thin films. Furthermore, this approach opens new opportunities for additional studies on the mechanisms and fundamentals of plasma polymer thin film formation with various monomers.