Special Issue "Polymers and Ionic Liquids: Shaping up a New Generation of High Performances Nanomaterials"

A special issue of Nanomaterials (ISSN 2079-4991).

Deadline for manuscript submissions: closed (15 March 2019).

Special Issue Editors

Prof. Dr. Jannick Duchet-Rumeau
Website
Guest Editor
Laboratoire Ingénierie des Matériaux Polymères (UMR 5223-http://www.imp.cnrs.fr/ ), INSA Lyon (www.insa-lyon.fr), 69100 Villeurbanne, France
Interests: processing of nanocomposites materials; processing of mesoporous materials with the use of carbon dioxide in supercritical medium as a foaming agent; processing of self-assembled materials onto inorganic surfaces with the use of phase separation phenomena in polymer blends and of self-organization phenomena (nanolithography, optical properties, etc.); processing of nanomaterials from ionic liquids; tailoring of interfaces/interphases in heterogeneous materials: polymer blends and fiber based composites
Prof. Dr. Jean-François Gérard
Website
Guest Editor
Ingénierie des Matériaux Polymères (IMP), CNRS UMR5223, INSA Lyon/Université de Lyon, 17 Jean Capelle Avenue, Villeurbanne, France
Interests: Soft matter; Nanostructured polymers and nanostructuration processes; Surfaces, interfaces and interphases/Multiphase polymer materials; Polymer-based composite materials; Polymer processing
Prof. Sébastien Livi
Website
Guest Editor
Laboratoire Ingénierie des Matériaux Polymères-Polymer Materials & Engineering Laboratory, Université de Lyon, CNRS, UMR 5223, Ingénierie des Matériaux Polymères, INSA Lyon, F-69621 Villeurbanne, France
Interests: synthesis of ionic liquids; nanomaterials from ionic liquids; polymeric ionic liquids; epoxy thermosets; polymer blends; biopolymers; functionalization of nanoparticles (solvent methods, supercritical carbon dioxide); polymer foaming (ScCO2); polymer composites; polymer nanocomposites
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Special Issue Information

Dear Colleagues,

In the last few years, the scientific community, including academic and industrial research, has put forward unprecedented efforts to develop new functional polymeric nanomaterials in terms of water or gas barriers, electrical, mechanical, fire retardancy, or self-healing properties.In order to achieve this, the introduction of organic–inorganic hybrids, based on silica, carbon nanotubes and layered silicates, or ionomers and block copolymers, have been widely reported in the literature. Very recently, ionic liquids that are organic salts have demonstrated their great potential as new components of advanced polymer materials. In fact, they can be used as interfacial agents of nanoparticles to develop high performance nanocomposites, as compatibilizing agents of polymer blends, as electrolytes in batteries, as flame retardant of polymer materials, as structuration and self-healing agents of thermoplastic and thermosets, and as processing aids of renewable resources. Thus, the main objective of this Special Issue is to highlight a glimpse of the real potential of ionic liquids in polymer nanoscience. 

Prof. Dr. Jannick Duchet-Rumeau
Prof. Dr. Jean-François Gérard
Prof. Dr. Sébastien Livi
Guest Editors

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Keywords

  • Ionic Liquids
  • Polymers nanocomposites
  • Multifunctional nanomaterials
  • Morphologies
  • Mechanical performances
  • Functional properties
  • Thermoplastics
  • Thermosets
  • Structure-property relationship

Published Papers (9 papers)

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Research

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Open AccessArticle
Ionic Liquid-Nanostructured Poly(Methyl Methacrylate)
Nanomaterials 2019, 9(10), 1376; https://doi.org/10.3390/nano9101376 - 26 Sep 2019
Abstract
Here, ionic liquids (ILs) based on imidazolium and ammonium cations were used as modifying agents for poly(methyl methacrylate) (PMMA) by extrusion. The effects of the chemical nature of the cation and/or counter anion on the resulting properties of IL-modified PMMA blends were analyzed. [...] Read more.
Here, ionic liquids (ILs) based on imidazolium and ammonium cations were used as modifying agents for poly(methyl methacrylate) (PMMA) by extrusion. The effects of the chemical nature of the cation and/or counter anion on the resulting properties of IL-modified PMMA blends were analyzed. It was found that the use of low amounts of ILs (2 wt.%) improved the thermal stability. A plasticizing effect of ILs is evidenced by a decrease in glass transition temperature Tg of the modified PMMA, allowing to get large strains at break (i.e., up to 280% or 400%) compared to neat PMMA. The deformation and fracture mechanisms of PMMA under uniaxial tensile stress (i.e., crazing) reveal that the presence of IL delayed the strain during the initiation step of crazing. Full article
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Open AccessArticle
New Insights on the Fast Response of Poly(Ionic Liquid)s to Humidity: The Effect of Free-Ion Concentration
Nanomaterials 2019, 9(5), 749; https://doi.org/10.3390/nano9050749 - 16 May 2019
Abstract
The swelling mechanism is widely used to explain the response of ionic liquids (ILs) or poly(ionic liquid)s (PILs) to moisture. While a fairly broad consensus has been attained, there are still some phenomena that are not well explained. As a complement to the [...] Read more.
The swelling mechanism is widely used to explain the response of ionic liquids (ILs) or poly(ionic liquid)s (PILs) to moisture. While a fairly broad consensus has been attained, there are still some phenomena that are not well explained. As a complement to the swelling mechanism, we systematically studied the free volume theory in the rapid response and recovery of PIL humidity performance. We chose poly(1-ethyl-3-vinylimidazolium bromide) (PIL-Br), poly(1-ethyl-3-vinylimidazolium tetrafluoroborate) (PIL-BF4) and poly(1-ethyl-3-vinylimidazolium bis(trifluoromethane sulfonimide)) (PIL-TFSI) as model materials and investigated the impact of PIL structure including anion type, film thickness and affinity to moisture on performance to obtain the humidity sensing mechanism for PILs based on free volume theory. Hence, we can combine free volume theory with the designed PIL structures and their affinity with moisture to obtain a high concentration of free ions in PIL sensing films. Furthermore, the PIL humidity sensors also show fast, substantial impedance changes with changing humidity for real-time monitoring of the human respiratory rate due to a fast response and recovery performance. Therefore, our findings develop a new perspective to understand the humidity performance of PILs based on free volume theory, resulting in fast response and recovery properties realized by the rational design of PIL sensing films. Full article
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Open AccessArticle
Pressure-Dependent Confinement Effect of Ionic Liquids in Porous Silica
Nanomaterials 2019, 9(4), 620; https://doi.org/10.3390/nano9040620 - 16 Apr 2019
Cited by 4
Abstract
The effect of confining ionic liquids (ILs) such as 1-ethyl-3-methylimidazolium tetrafluoroborate [C2C1Im][BF4] or 1-butyl-3-methylimidazolium tetrafluoroborate [C4C1Im][BF4] in silica matrices was investigated by high-pressure IR spectroscopy. The samples were prepared via the [...] Read more.
The effect of confining ionic liquids (ILs) such as 1-ethyl-3-methylimidazolium tetrafluoroborate [C2C1Im][BF4] or 1-butyl-3-methylimidazolium tetrafluoroborate [C4C1Im][BF4] in silica matrices was investigated by high-pressure IR spectroscopy. The samples were prepared via the sol-gel method, and the pressure-dependent changes in the C–H absorption bands were investigated. No appreciable changes were observed in the spectral features when the ILs were confined in silica matrices under ambient pressure. That is, the infrared measurements obtained under ambient pressure were not sufficient to detect the interfacial interactions between the ILs and the porous silica. However, dramatic differences were observed in the spectral features of [C2C1Im][BF4] and [C4C1Im][BF4] in silica matrices under the conditions of high pressures. The surfaces of porous silica appeared to weaken the cation-anion interactions caused by pressure-enhanced interfacial IL-silica interactions. This confinement effect under high pressures was less obvious for [C4C1Im][BF4]. The size of the cations appeared to play a prominent role in the IL-silica systems. Full article
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Open AccessArticle
Ionic Liquids as Delaminating Agents of Layered Double Hydroxide during In-Situ Synthesis of Poly (Butylene Adipate-co-Terephthalate) Nanocomposites
Nanomaterials 2019, 9(4), 618; https://doi.org/10.3390/nano9040618 - 16 Apr 2019
Cited by 1
Abstract
Currently, highly demanded biodegradable or bio-sourced plastics exhibit inherent drawbacks due to their limited processability and end-use properties (barrier, mechanical, etc.). To overcome all of these shortcomings, the incorporation of lamellar inorganic particles, such as layered double hydroxides (LDH) seems to be appropriate. [...] Read more.
Currently, highly demanded biodegradable or bio-sourced plastics exhibit inherent drawbacks due to their limited processability and end-use properties (barrier, mechanical, etc.). To overcome all of these shortcomings, the incorporation of lamellar inorganic particles, such as layered double hydroxides (LDH) seems to be appropriate. However, LDH delamination and homogenous dispersion in a polymer matrix without use of harmful solvents, remains a challenging issue, which explains why LDH-based polymer nanocomposites have not been scaled-up yet. In this work, LDH with intercalated ionic liquid (IL) anions were synthesized by a direct co-precipitation method in the presence of phosphonium IL and subsequently used as functional nanofillers for in-situ preparation of poly (butylene adipate-co-terephthalate) (PBAT) nanocomposites. The intercalated IL-anions promoted LDH swelling in monomers and LDH delamination during the course of in-situ polycondensation, which led to the production of PBAT/LDH nanocomposites with intercalated and exfoliated morphology containing well-dispersed LDH nanoplatelets. The prepared nanocomposite films showed improved water vapor permeability and mechanical properties and slightly increased crystallization degree and therefore can be considered excellent candidates for food packaging applications. Full article
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Open AccessArticle
A Cross-Linker-Based Poly(Ionic Liquid) for Sensitive Electrochemical Detection of 4-Nonylphenol
Nanomaterials 2019, 9(4), 513; https://doi.org/10.3390/nano9040513 - 02 Apr 2019
Cited by 2
Abstract
In this study, we report a cross-linker-based poly(ionic liquid) (PIL) for the sensitive detection of 4-nonylphenol (4-NP). PIL was poly(1,4-butanediyl-3,3′-bis-l-vinylimidazolium dibromide) (poly([V2C4(mim)2]Br2)). Poly([V2C4(mim)2]Br2) was prepared via one-step [...] Read more.
In this study, we report a cross-linker-based poly(ionic liquid) (PIL) for the sensitive detection of 4-nonylphenol (4-NP). PIL was poly(1,4-butanediyl-3,3′-bis-l-vinylimidazolium dibromide) (poly([V2C4(mim)2]Br2)). Poly([V2C4(mim)2]Br2) was prepared via one-step free-radical polymerization. The poly([V2C4(mim)2]Br2) was characterized by infrared spectroscopy, Raman spectroscopy, thermal gravimetric analyzer and scanning electron microscope. The poly([V2C4(mim)2]Br2) was then drop-cast onto a glassy carbon electrode (GCE) to obtain poly([V2C4(mim)2]Br2)/GCE. In comparison with a bare GCE, poly([V2C4(mim)2]Br2)/GCE exhibited higher peak current responses for [Fe(CN)6]3−/4−, lower charge transfer resistance, and larger effective surface area. While comparing the peak current responses, we found the peak current response for 4-NP using poly([V2C4(mim)2]Br2)/GCE to be 3.6 times higher than a traditional cross-linker ethylene glycol dimethacrylate (EGDMA) based poly(EGDMA) modified GCE. The peak current of poly([V2C4(mim)2]Br2) sensor was linear to 4-NP concentration from 0.05 to 5 μM. The detection limit of 4-NP was obtained as 0.01 μM (S/N = 3). The new PIL based electrochemical sensor also exhibited excellent selectivity, stability, and reusability. Furthermore, the poly([V2C4(mim)2]Br2)/GCE demonstrated good 4-NP detection in environmental water samples. Full article
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Open AccessArticle
Construction of Novel Polymerizable Ionic Liquid Microemulsions and the In Situ Synthesis of Poly(Ionic Liquid) Adsorbents
Nanomaterials 2019, 9(3), 454; https://doi.org/10.3390/nano9030454 - 18 Mar 2019
Cited by 6
Abstract
This paper reports the successful construction of novel polymerizable ionic liquid microemulsions and the in situ synthesis of poly(ionic liquid) adsorbents for the removal of Zn2+ from aqueous solution. Dynamic light-scattering data were used to confirm the polymerization media and to illustrate [...] Read more.
This paper reports the successful construction of novel polymerizable ionic liquid microemulsions and the in situ synthesis of poly(ionic liquid) adsorbents for the removal of Zn2+ from aqueous solution. Dynamic light-scattering data were used to confirm the polymerization media and to illustrate the effect of the crosslinker dosage on the droplet size of the microemulsion. FTIR and thermal analysis were employed to confirm the successful preparation of the designed polymers and characterize their thermostability and glass transition-temperature value. The optimization of the adsorption process indicates that the initial concentration of Zn2+, pH, adsorbent dosage and contact time affected the adsorption performance of poly(ionic liquid)s toward Zn2+. Furthermore, our research revealed that the adsorption process can be effectively described by the pseudo second-order kinetic model and the Freundlich isotherm model. Full article
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Open AccessArticle
Investigation on the Crystallization Behaviors of Polyoxymethylene with a Small Amount of Ionic Liquid
Nanomaterials 2019, 9(2), 206; https://doi.org/10.3390/nano9020206 - 05 Feb 2019
Cited by 1
Abstract
Polyoxymethylene (POM) blends with excellent stiffness–toughness balance are successfully developed using Tributyl(octyl)phosphonium bis(trifloromethanesulfonyl) imide (TBOP-TFSI), one type of room-temperature ionic liquid, as the nucleating agent. Crystallization behaviors of POM blends have been studied by differential scanning calorimetry (DSC) and polarized light microscopy (PLM). [...] Read more.
Polyoxymethylene (POM) blends with excellent stiffness–toughness balance are successfully developed using Tributyl(octyl)phosphonium bis(trifloromethanesulfonyl) imide (TBOP-TFSI), one type of room-temperature ionic liquid, as the nucleating agent. Crystallization behaviors of POM blends have been studied by differential scanning calorimetry (DSC) and polarized light microscopy (PLM). The incorporation of TBOP-TFSI induces the crystal nucleation and fine crystal grain of POM, and also a much shorter hemi-crystalline time with only 0.5 wt% addition. The nucleation effect of ionic liquid leads to considerable improvement in the impact strength of POM blends while not sacrificing its tensile strength. Moreover, antistatic properties with a long-time stable performance are achieved by TBOP-TFSI addition as the electrical resistance reaches 1011 Ω/sq. Full article
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Open AccessArticle
Gelled Electrolyte Containing Phosphonium Ionic Liquids for Lithium-Ion Batteries
Nanomaterials 2018, 8(6), 435; https://doi.org/10.3390/nano8060435 - 14 Jun 2018
Cited by 7
Abstract
In this work, new gelled electrolytes were prepared based on a mixture containing phosphonium ionic liquid (IL) composed of trihexyl(tetradecyl)phosphonium cation combined with bis(trifluoromethane)sulfonimide [TFSI] counter anions and lithium salt, confined in a host network made from an epoxy prepolymer and amine hardener. [...] Read more.
In this work, new gelled electrolytes were prepared based on a mixture containing phosphonium ionic liquid (IL) composed of trihexyl(tetradecyl)phosphonium cation combined with bis(trifluoromethane)sulfonimide [TFSI] counter anions and lithium salt, confined in a host network made from an epoxy prepolymer and amine hardener. We have demonstrated that the addition of electrolyte plays a key role on the kinetics of polymerization but also on the final properties of epoxy networks, especially thermal, thermo-mechanical, transport, and electrochemical properties. Thus, polymer electrolytes with excellent thermal stability (>300 °C) combined with good thermo-mechanical properties have been prepared. In addition, an ionic conductivity of 0.13 Ms·cm−1 at 100 °C was reached. Its electrochemical stability was 3.95 V vs. Li0/Li+ and the assembled cell consisting in Li|LiFePO4 exhibited stable cycle properties even after 30 cycles. These results highlight a promising gelled electrolyte for future lithium ion batteries. Full article
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Review

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Open AccessReview
New Developments in Material Preparation Using a Combination of Ionic Liquids and Microwave Irradiation
Nanomaterials 2019, 9(4), 647; https://doi.org/10.3390/nano9040647 - 22 Apr 2019
Cited by 4
Abstract
During recent years, synthetic methods combining microwaves and ionic liquids became accepted as a promising methodology for various materials preparations because of their high efficiency and low energy consumption. Ionic liquids with high polarity are heated rapidly, volumetrically and simultaneously under microwave irradiation. [...] Read more.
During recent years, synthetic methods combining microwaves and ionic liquids became accepted as a promising methodology for various materials preparations because of their high efficiency and low energy consumption. Ionic liquids with high polarity are heated rapidly, volumetrically and simultaneously under microwave irradiation. Hence, combination of microwave irradiation as a heating source with ionic liquids with various roles (e.g., solvent, additive, template or reactant) opened a completely new technique in the last twenty years for nanomaterials and polymers preparation for applications in various materials science fields including polymer science. This review summarizes recent developments of some common materials syntheses using microwave-assisted ionic liquid method with a focus on inorganic nanomaterials, polymers, carbon-derived composites and biomass-based composites. After that, the mechanisms involved in microwave-assisted ionic-liquid (MAIL) are discussed briefly. This review also highlights the role of ionic liquids in the reaction and crucial issues that should be addressed in future research involving this synthesis technique. Full article
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