Dynamic mechanical thermal and infrared analyses of polyacrylonitrile ?electrografted? onto a metal

Calberg, Cédric; Mertens, Martine; Baute, Noëlle; Jérôme, Robert; Carlier, Vincent; Sclavons, Michel; Legras, Roger

doi:10.1002/(sici)1099-0488(199803)36:4<543::aid-polb1>3.0.co;2-q

Cited by 13 publications

(13 citation statements)

References 11 publications

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“…(ii) Dynamic mechanical thermal analyses (DMTA) recently performed by some of us [15] on PAN thin films, are in favor of a two-step AN electroreduction mechanism (Fig. 1), since the grafted polymer formed at the potential of peak I has not the same properties as the ungrafted one formed at the more negative potential (peak II).…”

Section: Introductionmentioning

confidence: 99%

Solvent effect on the electrografting of acrylonitrile on nickel

Mertens

Calberg

Baute

et al. 1998

Journal of Electroanalytical Chemistry

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The effect of solvent on the reductive electrografting of acrylonitrile (AN) onto nickel cathodes has been studied in dimethylformamide (DMF), a solvent for polyacrylonitrile (PAN), and in non-solvents that include acetonitrile (ACN), propylene carbonate (PC) and pyridine (PY). Electrografting responsible for the cathode inhibition has been observed for the first time in PC and PY. Not only the polymer-solvent interactions but also the intrinsic polarity of the solvent have an effect on the intensity of the inhibition peak which is the signature of the electrografting reaction. Concentration of the monomer in the electrode double layer appears to decrease as the solvent polarity is increased, consistently with a more efficient displacement of the monomer by a more polar compound. That such a competition occurs is also supported by the effect of the nature and concentration of the conducting salt. The best quality films are formed in DMF, which is a solvent for PAN. Quarts: microbalance experiments have emphasized the crucial importance of the potential range used for the AN electroreduction, particularly in a solvent of the polymer.

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Section: Introductionmentioning

confidence: 99%

Solvent effect on the electrografting of acrylonitrile on nickel

Mertens

Calberg

Baute

et al. 1998

Journal of Electroanalytical Chemistry

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“…However, these chains are completely desorbed when the surface is immersed in an electrolytic solution (without monomer) and cathodically polarized in the range of the second voltammetric peak. The isotacticity of these chains was experimentally confirmed by dynamic mechanical analysis and infrared spectroscopy [62]. As far as PAN is concerned, Fourier transform infrared (FTIR) analysis [58] also confirmed the absence of cross-linking, which had, however, been suggested earlier [59][60][61].…”

Section: (Meth)acrylic Monomersmentioning

confidence: 79%

Covalent Bonding of Functional Coatings on Conductive Materials: the Electrochemical Approach

Cécius¹,

Jérôme²

2011

Handbook of Stimuli‐Responsive Materials

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IntroductionThis chapter describes electrochemical approaches to achieve functional organic coatings of metals, carbon, and semiconductors, and discusses the advantages and limitations in the development of the emerging strategies, particularly focusing on examples of smart or stimuli-responsive polymer coatings. The various strategies are classified on the basis of the strength of the coating/metal interactions, starting with simply deposited coatings and then describing chemisorbed films.In the recent past, the coating of (semi)conductive inorganic materials such as metals (Au, Ag, Pt, Fe, Cu, etc.), carbon (glassy carbon, felt, microfibers, nanotubes, etc.), or semiconductors (doped Si, metal oxides, etc.) by an organic layer has attracted considerable attention because of the emergence of rapidly growing, very demanding fields such as nanotechnologies and biomedical sciences. Indeed, the wide versatility of organic and polymer chemistries allows to produce innovative coatings, such as stimuli-responsive coatings, that are of interest in the modification of surface properties of conductive materials. In particular, functional and/or responsive coatings are needed for applications such as solar cells, (bio)sensors, and biomedical implants. In addition, increasing concern about the environment tends to restrict the technologies and products to the greenest ones. Under these novel driving forces, efficient methods for the surface modification of conducting inorganic materials by polymer coatings are being developed.For the coating of conductive or semiconductive materials, one can take advantage of their electrochemical properties to control, master, and localize the coating and its adhesion to the substrate by applying an electrochemical treatment to the substrate under well-defined conditions.Electrochemical methods are easily applied and rapid, and are already widely used in industry. They can be often performed in aqueous media from readily available organic precursors and require relatively low energy. This technology thus appears really relevant in many cases in the creation of thin polymer films on (semi)conductors in possible greener conditions.

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“…The IR spectrum of the xylene-insoluble fraction also has absorption bands from 1 590 to 1 780 cm À1 , possibly involving several vinyl functionalities due to cyclization and aromatization reactions (forming cyclic imines) that may take place during Soxhlet extraction at high temperature. [23] Figure 2 shows that the intensity of the nitrile bands differ among Samples 4, 5, and 6, proportionally to the concentration of acrylonitrile used in the polymerization. As expected, samples made with higher acrylonitrile concentrations have a more pronounced 2 245 cm À1 band.…”

Section: Chemical Analysesmentioning

confidence: 99%

Synthesis of Ethylene/Acrylonitrile Composite Elastomers with Nanosized Polyacrylonitrile Domains Using α‐Dimine‐[N,N] Nickel Dichloride/EASC

Shin

Simon

Soares

2011

Macro Chemistry & Physics

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A series of ethylene and acrylonitrile composite elastomers were prepared using (1,4‐bis(2,6diisopropylphenyl)‐acenaphtenediimine‐nickel(II))‐dichloride/ethylaluminum sesquichloride (EASC). The xylene‐soluble polymer fraction showed nitrile bands in infrared spectroscopy at 2 245 and 2 214 cm−1 and polyacrylonitrile‐enriched structures were detected in the xylene‐insoluble fraction by1H and 13C NMR. In addition, TEM detected nanosized polyacrylonitrile domains dispersed in the polyethylene matrix. Differential scanning calorimetry scans conducted from −70 to 350 °C measured exothermic bands corresponding to the cyclization and aromatization of the nitrile groups dispersed in the polyethylene matrix. magnified image

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Dynamic mechanical thermal and infrared analyses of polyacrylonitrile ?electrografted? onto a metal

Cited by 13 publications

References 11 publications

Solvent effect on the electrografting of acrylonitrile on nickel

Solvent effect on the electrografting of acrylonitrile on nickel

Covalent Bonding of Functional Coatings on Conductive Materials: the Electrochemical Approach

Synthesis of Ethylene/Acrylonitrile Composite Elastomers with Nanosized Polyacrylonitrile Domains Using α‐Dimine‐[N,N] Nickel Dichloride/EASC

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