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Nanomaterials
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Ionic Interfaces in Smart Polymer Materials
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Ionic Interfaces in Smart Polymer Materials

A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Synthesis, Interfaces and Nanostructures".

Deadline for manuscript submissions: closed (31 January 2022) | Viewed by 11214

Special Issue Editors

Dr. Sébastien Livi

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Guest Editor
Ingénierie des Matériaux Polymères, Université de Lyon, CNRS, UMR 5223, INSA Lyon, F-69621 Villeurbanne, France
Interests: ionic liquids; nanocomposites; ionic liquid monomers; epoxy thermosets; composites; recycling of thermosets; polymer-ionic liquid materials
Special Issues, Collections and Topics in MDPI journals
Dr. Ricardo Keitel Donato

E-Mail Website
Guest Editor
Centre for Advanced 2D Materials (CA2DM)-National University of Singapore, 6 Science Drive 2, Singapore 117546, Singapore
Interests: 2D materials-based polymer composites and blends; ionic interphases in polymer blends and composites; self-assembling nanomaterials; biopolymer-based composites and blends
Special Issues, Collections and Topics in MDPI journals
Dr. Hynek Beneš

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Guest Editor
Institute of Macromolecular Chemistry of the Academy of Sciences of the Czech Republic, Prague, Czech Republic
Interests: microwave-assisted synthesis of polymers and nanocomposites; ionic liquids; epoxy nanomaterials; bio-based and biodegradable polymers; polyurethane synthesis and degradation
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Materials sciences have a major role in meeting the current global challenges such as environmental stewardship; the production, storage, and conversion of energy; and cost-effective transportation, leading the research to design advanced polymer materials that consider both their shelf- and end-of-life. Through the concept “function through structural design”, the development of easy and new production methods is crucial for preparing innovative polymer material solutions and thus ensures a sustainable future. Consequently, in recent years, the polymer materials community has put a great deal of effort into designing innovative polymer materials that are engineered to be multifunctional or task-specific, presenting enhancement in properties such as ionic conductivity, chemical and thermal stability, mechanical performance, fire retardancy, barrier properties, self-healing ability, and shape memory behavior. This can be effectively achieved by altering the interphase behavior of these polymer systems, both via chemical modification or incorporating additives/fillers such as block copolymers, ionomers, organic–inorganic hybrid materials, or inorganic-rich nano-objects. Among these, the application of (poly)ionic liquids, eutectic solvents, and eutectic molecular liquids have presented many new opportunities within the last decade, since small amounts of these compounds can impart dramatic interphase modifications to polymer materials due the production of vast physical interphase bonding, including the formation of ionic bonding. Especially considering their unique set of physico-chemical properties as well as their multitude of chemical structures, they represent a promising new path to designing and creating new multifunctional and task-specific polymeric materials.

Prof. Dr. Sébastien Livi
Dr. Ricardo Keitel Donato
Dr. Hynek Beneš
Guest Editors

Manuscript Submission Information

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Keywords

  • interphase
  • interfacial agents
  • shape memory behavior
  • functional properties
  • (poly)ionic liquids
  • polymer blends
  • nanocomposites

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Published Papers (5 papers)

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Research

16 pages, 2149 KiB  
Article
Water Uptake in Epoxy Ionic Liquid Free Film Polymer by Gravimetric Analysis and Comparison with Nondestructive Dielectric Analysis
by Lucas Ollivier-Lamarque, Sébastien Livi, Tetsuya Uchimoto and Nicolas Mary
Nanomaterials 2022, 12(4), 651; https://doi.org/10.3390/nano12040651 - 15 Feb 2022
Cited by 5 | Viewed by 2070
Abstract
Due to their high surface coverage, good adhesion to metal surfaces, and their excellent corrosion resistance, epoxy thermosets are widely used as protective coatings. However, anticorrosion protection of these coatings can be improved against water uptake and can be tuned by changing the [...] Read more.
Due to their high surface coverage, good adhesion to metal surfaces, and their excellent corrosion resistance, epoxy thermosets are widely used as protective coatings. However, anticorrosion protection of these coatings can be improved against water uptake and can be tuned by changing the chemical nature of the curing agents. In this work, a comparative study has been performed on the water uptake of an epoxy–amine based on bisphenol A diglycidyl ether (DGEBA) cured with an aliphatic amine and the same epoxy initiated with a phosphonium ionic liquid (IL). Thus, the epoxy networks were immersed in saline water solution in a controlled temperature environment. Gravimetric and electric impedance measurements were carried out for a maximum of 3 months. Results were analyzed in order to assess the water diffusion coefficients and water saturation limits. Two models, the Brasher–Kingsbury and a novel mixing rule, were applied on permittivity values. Results highlighted that epoxy–ionic liquid systems are less sensitive to water uptake than conventional epoxy–amine networks. Due to their higher hydrophobic properties the water diffusion coefficient of epoxy–ionic liquid systems are two times less compared to epoxy–amine samples and the water saturation limit is more than four times less. The analysis also shows that the novel mixing rule model proposed here is prone to better estimate the water uptake with accuracy from electrical impedance measurements. Full article
(This article belongs to the Special Issue Ionic Interfaces in Smart Polymer Materials)
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20 pages, 5637 KiB  
Article
New Epoxy Thermosets Organic-Inorganic Hybrid Nanomaterials Derived from Imidazolium Ionic Liquid Monomers and POSS®Ph
by Houssém Chabane, Sébastien Livi, Jannick Duchet-Rumeau and Jean-François Gérard
Nanomaterials 2022, 12(3), 550; https://doi.org/10.3390/nano12030550 - 6 Feb 2022
Cited by 2 | Viewed by 2436
Abstract
New epoxy-amine networks issue from epoxydized imidazolium ionic liquid monomers (ILMs) and isophorone diamine (IPD) were modified for the first time by incorporating unmodified trisilanol phenyl POSS® (POSS®Ph-triol) and two ionic liquid-modified POSS®Ph (IL-g-POSS®Ph) having chloride (Cl [...] Read more.
New epoxy-amine networks issue from epoxydized imidazolium ionic liquid monomers (ILMs) and isophorone diamine (IPD) were modified for the first time by incorporating unmodified trisilanol phenyl POSS® (POSS®Ph-triol) and two ionic liquid-modified POSS®Ph (IL-g-POSS®Ph) having chloride (Cl−) and bis-trifluoromethanesulfonimidate (NTf2−) counter anions. Then, 5 wt.% of unmodified and IL-modified POSS®Ph were introduced in order to develop new solid electrolytes. First, a homogeneous dispersion of the POSS®Ph aggregates (diameters from 80 to 400 nm) into epoxy networks was observed. As a consequence, ILM/IPD networks with glass transition temperatures between 45 and 71 °C combined with an enhancement of the thermal stability (>380 °C) were prepared. Moreover, a significant increase of the hydrophobic character and high oil repellency of the network surfaces were obtained by using IL-g-POSS®Ph (19–20 mJ.m−2), opening up promising prospects for surface coating applications. Finally, these new epoxy networks exhibited outstanding high ionic conductivities (from 3.4 × 10−8 to 6.8 × 10−2 S.m−1) combined with an increase in permitivity. Full article
(This article belongs to the Special Issue Ionic Interfaces in Smart Polymer Materials)
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21 pages, 10011 KiB  
Article
Epoxy/Ionic Liquid-Modified Mica Nanocomposites: Network Formation–Network Degradation Correlation
by Maryam Jouyandeh, Vahideh Akbari, Seyed Mohammad Reza Paran, Sébastien Livi, Luanda Lins, Henri Vahabi and Mohammad Reza Saeb
Nanomaterials 2021, 11(8), 1990; https://doi.org/10.3390/nano11081990 - 3 Aug 2021
Cited by 12 | Viewed by 2843
Abstract
We synthesized pristine mica (Mica) and N-octadecyl-N’-octadecyl imidazolium iodide (IM) modified mica (Mica-IM), characterized it, and applied it at 0.1–5.0 wt.% loading to prepare epoxy nanocomposites. Dynamic differential scanning calorimetry (DSC) was carried out for the analysis of the cure potential and kinetics [...] Read more.
We synthesized pristine mica (Mica) and N-octadecyl-N’-octadecyl imidazolium iodide (IM) modified mica (Mica-IM), characterized it, and applied it at 0.1–5.0 wt.% loading to prepare epoxy nanocomposites. Dynamic differential scanning calorimetry (DSC) was carried out for the analysis of the cure potential and kinetics of epoxy/Mica and epoxy/Mica-IM curing reaction with amine curing agents at low loading of 0.1 wt.% to avoid particle aggregation. The dimensionless Cure Index (CI) was used for qualitative analysis of epoxy crosslinking in the presence of Mica and Mica-IM, while qualitative cure behavior and kinetics were studied by using isoconversional methods. The results indicated that both Mica and Mica-IM improved the curability of epoxy system from a Poor to Good state when varying the heating rate in the interval of 5–15 °C min−1. The isoconversional methods suggested a lower activation energy for epoxy nanocomposites with respect to the blank epoxy; thus, Mica and Mica-IM improved crosslinking of epoxy. The higher order of autocatalytic reaction for epoxy/Mica-IM was indicative of the role of liquid crystals in the epoxide ring opening. The glass transition temperature for nanocomposites containing Mica and Mica-IM was also lower than the neat epoxy. This means that nanoparticles participated the reaction because of being reactive, which decelerated segmental motion of the epoxy chains. The kinetics of the thermal decomposition were evaluated for the neat and mica incorporated epoxy nanocomposites epoxy with varying Mica and Mica-IM amounts in the system (0.5, 2.0 and 5.0 wt.%) and heating rates. The epoxy/Mica-IM at 2.0 wt.% of nanoparticle showed the highest thermal stability, featured by the maximum value of activation energy devoted to the assigned system. The kinetics of the network formation and network degradation were correlated to demonstrate how molecular-level transformations can be viewed semi-experimentally. Full article
(This article belongs to the Special Issue Ionic Interfaces in Smart Polymer Materials)
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27 pages, 19340 KiB  
Article
Investigation of the Ionic Liquid Graphene Electric Double Layer in Supercapacitors Using Constant Potential Simulations
by Baris Demir and Debra J. Searles
Nanomaterials 2020, 10(11), 2181; https://doi.org/10.3390/nano10112181 - 1 Nov 2020
Cited by 28 | Viewed by 4293
Abstract
In this work, we investigate the effect of the cation structure on the structure and dynamics of the electrode–electrolyte interface using molecular dynamics simulations. A constant potential method is used to capture the behaviour of 1-ethyl-3-methylimidazolium bis (trifluoromethane)sulfonimide ([C2mim][NTf2]) [...] Read more.
In this work, we investigate the effect of the cation structure on the structure and dynamics of the electrode–electrolyte interface using molecular dynamics simulations. A constant potential method is used to capture the behaviour of 1-ethyl-3-methylimidazolium bis (trifluoromethane)sulfonimide ([C2mim][NTf2]) and butyltrimethylammonium bis(trifluoromethane) sulfonimide ([N4,1,1,1][NTf2]) ionic liquids at varying potential differences applied across the supercapacitor. We find that the details of the structure in the electric double layer and the dynamics differ significantly, yet the charge profile and capacitance do not vary greatly. For the systems considered, charging results in the rearrangement and reorientation of ions within ∼1 nm of the electrode rather than the diffusion of ions to/from the bulk region. This occurs on timescales of O(10 ns) for the ionic liquids considered, and depends on the viscosity of the fluid. Full article
(This article belongs to the Special Issue Ionic Interfaces in Smart Polymer Materials)
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14 pages, 1564 KiB  
Article
Effects of Immobilized Ionic Liquid on Properties of Biodegradable Polycaprolactone/LDH Nanocomposites Prepared by In Situ Polymerization and Melt-Blending Techniques
by Sonia Bujok, Jiří Hodan and Hynek Beneš
Nanomaterials 2020, 10(5), 969; https://doi.org/10.3390/nano10050969 - 18 May 2020
Cited by 18 | Viewed by 2949
Abstract
The high capacity of calcinated layered double hydroxides (LDH) to immobilize various active molecules together with their inherent gas/vapor impermeability make these nanoparticles highly promising to be applied as nanofillers for biodegradable polyester packaging. Herein, trihexyl(tetradecyl)phosphonium decanoate ionic liquid (IL) was immobilized on [...] Read more.
The high capacity of calcinated layered double hydroxides (LDH) to immobilize various active molecules together with their inherent gas/vapor impermeability make these nanoparticles highly promising to be applied as nanofillers for biodegradable polyester packaging. Herein, trihexyl(tetradecyl)phosphonium decanoate ionic liquid (IL) was immobilized on the surface of calcinated LDH. Thus, the synthesized nanoparticles were used for the preparation of polycaprolactone (PCL)/LDH nanocomposites. Two different methods of nanocomposite preparation were used and compared: microwave-assisted in situ ring opening polymerization (ROP) of ε-caprolactone (εCL) and melt-blending. The in situ ROP of εCL in the presence of LDH nanoparticles with the immobilized IL led to homogenous nanofiller dispersion in the PCL matrix promoting formation of large PCL crystallites, which resulted in the improved mechanical, thermal and gas/water vapor barrier properties of the final nanocomposite. The surface-bonded IL thus acted as nanofiller surfactant, compatibilizer, as well as thermal stabilizer of the PCL/LDH nanocomposites. Contrary to that, the melt-blending caused a partial degradation of the immobilized IL and led to the production of PCL nanocomposites with a heterogenous nanofiller dispersion having inferior mechanical and gas/water vapor barrier properties. Full article
(This article belongs to the Special Issue Ionic Interfaces in Smart Polymer Materials)
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