Oxidative chemical vapor deposition of polypyrrole onto carbon fabric for flexible supercapacitive electrode material

Polypyrrole has been a promising conjugated polymer for application in electrochemical energy storage devices. One primary feature is its pseudocapacitive behavior, which makes it suitable for hybridization with traditional carbon-based electrical double layer capacitive materials. The processing condition for such a hybridization is a critical aspect for the electrode performance in long term. Oxidative chemical vapor deposition was used to deposit polypyrrole onto 3D carbon fiber fabric. This allowed uniform and conformal deposition of polypyrrole on individual fibers as well as a control over its thickness depending on the reaction time. The obtained composite was characterized for electrochemical energy storage application using cyclic voltammetry and galvanostatic charge discharge measurements. Additionally, the stability of the polypyrrole-carbon fiber electrode was tested using microscopy and energy dispersive spectroscopy in order to obtain insights into physical and chemical degradation of polypyrrole during electrochemical aging. Results showed thickness-dependence of electrode stability, tuning of which in the correct voltage window is necessary for optimal long-term performance

Thermoreversible Polymeric Nanocomposites

Polymeric nanocomposites are widely used in applications such as structural materials, electronics, energy, and biomedical as they synergistically combine the desired properties of the filler and the polymer. The emergent properties can be designed and tuned based not only on the choice of filler and polymer but also on the type of bond and interface created between the two components. When the bond between the two is covalent, the nanocomposites have superior mechanical characteristics. When this covalent bond is reversible, a combination of high impact resistance and high tensile strength is achieved. A well-known approach to achieve these reversible covalent bonds is via the Diels-Alder reaction between a diene and a dienophile. At elevated temperatures, the retro Diels-Alder reaction is dominant resulting in bond cleavage. This chapter reviews the different strategies involving Diels-Alder reactions at the polymer-filler interface. Various fillers have been researched including silica, carbon nanotubes, and graphene, which impart different mechanical and conductive properties to the nanocomposite. A variety of polymer matrices have been reported by various researchers and are summarized here. The choice of diene and dienophile influences the rate of reversible reaction and thus the final properties as will be discussed

Electrically and thermally healable nanocomposites via one-step Diels-Alder reaction on carbon nanotubes

Carbon nanotubes (CNTs) were directly employed as reactive fillers in furan-pendant polyketones via the Diels-Alder (DA) reaction. CNTs and furan groups function as dienophile and diene, respectively, forming a reversible crosslinking network. Here, pristine CNTs not only serve as crosslinking agents, but also improve the thermal and electrical conductivity. The DA covalent linkage was confirmed by IR, TGA, DSC, elemental analysis and dispersion tests. This one-step approach offers a facile route to synthesize reversibly crosslinked thermoset polymer nanocomposites. The rigidity of the nanocomposites could be controlled through the number of furan groups in order to achieve distinct properties. The nanocomposites demonstrated dynamic temperature-dependent behavior due to the retro Diels-Alder reaction. Cyclic tests via rheology showed good reversibility below 120 °C. However, an irreversible increase of modulus was observed at higher temperatures, which is possibly attributed to a side reaction. At filler loadings above 5%, both electrical and thermal self-healing tests showed good results. The Diels-Alder reaction between CNTs and furan-pendant polymers opens up a new possibility of directly employing fillers in the polymer matrix without any prior modifications. It is also possible to use other fillers with diene/dienophile properties in future reversible polymer nanocomposites

Highly Branched Waxy Potato Starch-Based Polyelectrolyte:Controlled Synthesis and the Influence of Chain Composition on Solution Rheology

In the present work, a series of highly branched random copolymers of acrylamide (AM), sodium 2-acrylamido-2-methyl-1-propanesulfonate (SAMPS), and N-isopropylacrylamide (NIPAM) were prepared by using water-soluble waxy potato starch-based macroinitiator via aqueous Cu0-mediated living radical polymerization (25 °C). The AM/SAMPS/NIPAM ratio was varied to investigate the influence of chain composition on the aqueous rheological properties of the prepared copolymers. Rheological results indicated an optimum SAMPS intake (25 mol %) for the balanced performance of viscosity and salt resistance in saline water. The intake of NIPAM units (e.g., 25 mol %), contrary to what was expected, undermines the thickening ability of the copolymers in saline water because of hydrophobic association. In high salinity solution, thermo-thickening behavior can be observed at low shear rates (γ≤ 3 s-1) because of the screening effect of salt on the negatively charged SAMPS units. At the high shear rate, the thermo-thickening behavior disappears because of the disruption of the NIPAM aggregates. These results pave the way toward the use of the prepared polymers as rheology modifiers in a variety of possible formulations for different applications, in particular in enhanced oil recovery

Designing End-of-life Recyclable Polymers via Diels-Alder Chemistry:A Review on the Kinetics of Reversible Reactions

The purpose of this review is to critically assess the kinetic behaviour of the furan/maleimide Diels-Alder click reaction. The popularity of this reaction is evident and still continues to grow, which is likely attributed to its reversibility at temperatures above 100°C, and due to its bio-based "roots" in terms of raw materials. This chemistry has been used to form thermo-reversible crosslinks in polymer networks, and thus allows the polymer field to design strong, but also end-of-life recyclable thermosets and rubbers. In this context, the rate at which the forward reaction (Diels-Alder for crosslinking) and its reverse (retro Diels-Alder for de-crosslinking) proceed as function of temperature is of crucial importance in assessing the feasibility of the design in real-life products. Differences in kinetics based from various studies are not well understood, but are potentially caused by chemical side groups, mass transfer limitations, and on the analysis methods being employed. In this work we attempt to place all the relevant studies in perspective with respect to each other, and thereby offer a general guide on how to assess their recycling kinetics. This review sheds light on the kinetics on the furan/maleimide Diels-Alder reaction. This popular reaction opens up a path to develop end-of-life recyclable polymer networks with self-healing properties. The factors affecting reaction kinetics are discussed, and the importance of accurate reaction kinetics in the context of polymer reprocessing is highlighted. This article is protected by copyright. All rights reserved

Initiated Chemical Vapor Deposition (iCVD) of Bio-Based Poly(tulipalin A) Coatings:Structure and Material Properties

A solvent-free route of initiated chemical vapor deposition (iCVD) was used to synthesize a bio-renewable poly(α-Methylene-γ-butyrolactone) (PMBL) polymer. α-MBL, also known as tulipalin A, is a bio-based monomer that can be a sustainable alternative to produce polymer coatings with interesting material properties. The produced polymers were deposited as thin films on three different types of substrates—polycarbonate (PC) sheets, microscopic glass, and silicon wafers—and characterized via an array of characterization techniques, including Fourier-transform infrared (FTIR), proton nuclear magnetic resonance spectroscopy ((1)H NMR), ultraviolet visible spectroscopy (UV–vis), differential scanning calorimetry (DSC), size-exclusion chromatography (SEC), and thermogravimetric analysis (TGA). Optically transparent thin films and coatings of PMBL were found to have high thermal stability up to 310 °C. The resulting PMBL films also displayed good optical characteristics, and a high glass transition temperature (T(g)~164 °C), higher than the T(g) of its structurally resembling fossil-based linear analogue-poly(methyl methacrylate). The effect of monomer partial pressure to monomer saturation vapor pressure (P(m)/P(sat)) on the deposition rate was investigated in this study. Both the deposition rate and molar masses increased linearly with Pm/Psat following the normal iCVD mechanism and kinetics that have been reported in literature

Intrinsic Self-Healing Epoxies in Polymer Matrix Composites (PMCs) for Aerospace Applications

This article reviews some of the intrinsic self-healing epoxy materials that have been investigated throughout the course of the last twenty years. Emphasis is placed on those formulations suitable for the design of high-performance composites to be employed in the aerospace field. A brief introduction is given on the advantages of intrinsic self-healing polymers over extrinsic counterparts and of epoxies over other thermosetting systems. After a general description of the testing procedures adopted for the evaluation of the healing efficiency and the required features for a smooth implementation of such materials in the industry, different self-healing mechanisms, arising from either physical or chemical interactions, are detailed. The presented formulations are critically reviewed, comparing major strengths and weaknesses of their healing mechanisms, underlining the inherent structural polymer properties that may affect the healing phenomena. As many self-healing chemistries already provide the fundamental aspects for recyclability and reprocessability of thermosets, which have been historically thought as a critical issue, perspective trends of a circular economy for self-healing polymers are discussed along with their possible advances and challenges. This may open up the opportunity for a totally reconfigured landscape in composite manufacturing, with the net benefits of overall cost reduction and less waste. Some general drawbacks are also laid out along with some potential countermeasures to overcome or limit their impact. Finally, present and future applications in the aviation and space fields are portrayed

Synthesis of zwitterionic copolymers via copper-mediated aqueous living radical grafting polymerization on starch

[2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA) is a well-studied sulfobetaine-methacrylate as its zwitterionic structure allows the synthesis of polymers with attractive properties like antifouling and anti-polyelectrolyte behavior. In the present work, we report the Cu0-mediated living radical polymerization (Cu0-mediated LRP) of SBMA in sodium nitrate aqueous solution instead of previously reported solvents like trifluoroethanol and sodium chloride aqueous/alcoholic solution. Based on this, starch-g-polySBMA (St-g-PSBMA) was also synthesized homogeneously by using a water-soluble waxy potato starch-based macroinitiator and CuBr/hexamethylated tris(2-aminoethyl)amine (Me6TREN) as the catalyst. The structure of the macroinitiator was characterized by 1H-NMR, 13C-NMR, gHSQC, and FT-IR, while samples of PSBMA and St-g-PSBMA were characterized by 1H-NMR and FT-IR. Monomer conversion was monitored by 1H-NMR, on the basis of which the reaction kinetics were determined. Both kinetic study and GPC results indicate reasonable controlled polymerization. Furthermore, a preliminary study of the thermal response behavior was also carried through rheological tests performed on aqueous solutions of the prepared materials. Results show that branched zwitterionic polymers are more thermal-sensitive than linear ones.</p

Thermally Reversible Polymeric Networks from Vegetable Oils

Low cross-link density thermally reversible networks were successfully synthesized from jatropha and sunflower oils. The oils were epoxidized and subsequently reacted with furfurylamine to attach furan groups onto the triglycerides, preferably at the epoxide sites rather than at the ester ones. Under the same reaction conditions, the modified jatropha oil retained the triglyceride structure more efficiently than its sunflower-based counterpart, i.e., the ester aminolysis reaction was less relevant for the jatropha oil. These furan-modified oils were then reacted with mixtures of aliphatic and aromatic bismaleimides, viz. 1,12-bismaleimido dodecane and 1,10-(methylenedi-4,1-phenylene)bismaleimide, resulting in a series of polymers with Tg ranging between 3.6 and 19.8 °C. Changes in the chemical structure and mechanical properties during recurrent thermal cycles suggested that the Diels-Alder and retro-Diels-Alder reactions occurred. However, the reversibility was reduced over the thermal cycles due to several possible causes. There are indications that the maleimide groups were homopolymerized and the Diels-Alder adducts were aromatized, leading to irreversibly cross-linked polymers. Two of the polymers were successfully applied as adhesives without modifications. This result demonstrates one of the potential applications of these polymers

Cross-Linking of Polypropylene via the Diels-Alder Reaction

In this work, the possibility of preparing cross-linked polypropylene (PP) via Diels–Alder (DA) chemistry is explored. The overall strategy involves reaction of maleated polypropylene (the starting material), furfuryl amine (FFA), and bismaleimide (BM) as the cross-linking agent. The occurrence of reversible cross-linking was studied by checking the presence of relevant peaks in FTIR spectra, i.e., CH out-of-plane bending vibrations of the furan ring’s peak (γCH) at an absorption band of 730–734 cm(−1), CH=CH of the BM aromatic ring’s stretching vibrations (υCH=CH) at an absorption band of 1510 cm(−1), and the DA adduct (C-O-C, δDAring) at an absorption band of 1186 cm(−1). In agreement with the spectroscopic characterization, the presence of a cross-linked network is also confirmed by rheology, namely the higher storage modulus (G′) compared with loss modulus (G″) value (G′ >> G″), as obtained via temperature sweep. Both the maleic anhydride (MA) content as well as the annealing temperature (50 °C and 120 °C) favor the DA reaction, while only partial de-cross-linking (retro DA) is observed at the higher temperature range of 150–200 °C. In addition, the products show higher mechanical robustness and thermal stability compared to the starting material