Research

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16 pages, 3671 KiB

Open AccessArticle

Ionic Liquid-Nanostructured Poly(Methyl Methacrylate)

by Clarice Fedosse Zornio, Sébastien Livi, Jannick Duchet-Rumeau and Jean-François Gerard

Nanomaterials 2019, 9(10), 1376; https://doi.org/10.3390/nano9101376 - 26 Sep 2019

Cited by 15 | Viewed by 2920

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

(This article belongs to the Special Issue Polymers and Ionic Liquids: Shaping up a New Generation of High Performances Nanomaterials)

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15 pages, 5382 KiB

Open AccessArticle

New Insights on the Fast Response of Poly(Ionic Liquid)s to Humidity: The Effect of Free-Ion Concentration

by Jianxia Nie, Songhua Xiao, Rou Tan, Taihong Wang and Xiaochuan Duan

Nanomaterials 2019, 9(5), 749; https://doi.org/10.3390/nano9050749 - 16 May 2019

Cited by 12 | Viewed by 3232

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

(This article belongs to the Special Issue Polymers and Ionic Liquids: Shaping up a New Generation of High Performances Nanomaterials)

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13 pages, 1407 KiB

Open AccessArticle

Pressure-Dependent Confinement Effect of Ionic Liquids in Porous Silica

by Teng-Hui Wang, En-Yu Lin and Hai-Chou Chang

Nanomaterials 2019, 9(4), 620; https://doi.org/10.3390/nano9040620 - 16 Apr 2019

Cited by 13 | Viewed by 2744

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

(This article belongs to the Special Issue Polymers and Ionic Liquids: Shaping up a New Generation of High Performances Nanomaterials)

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16 pages, 4034 KiB

Open AccessArticle

Ionic Liquids as Delaminating Agents of Layered Double Hydroxide during In-Situ Synthesis of Poly (Butylene Adipate-co-Terephthalate) Nanocomposites

by Hynek Beneš, Jana Kredatusová, Jakub Peter, Sébastien Livi, Sonia Bujok, Ewa Pavlova, Jiří Hodan, Sabina Abbrent, Magdalena Konefał and Petra Ecorchard

Nanomaterials 2019, 9(4), 618; https://doi.org/10.3390/nano9040618 - 16 Apr 2019

Cited by 18 | Viewed by 3128

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

(This article belongs to the Special Issue Polymers and Ionic Liquids: Shaping up a New Generation of High Performances Nanomaterials)

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11 pages, 3325 KiB

Open AccessArticle

A Cross-Linker-Based Poly(Ionic Liquid) for Sensitive Electrochemical Detection of 4-Nonylphenol

by Jian Hu, Hao Dai, Yanbo Zeng, Yiwen Yang, Hailong Wang, Xudong Zhu, Lei Li, Guobao Zhou, Ruoyu Chen and Longhua Guo

Nanomaterials 2019, 9(4), 513; https://doi.org/10.3390/nano9040513 - 02 Apr 2019

Cited by 13 | Viewed by 3361

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

(This article belongs to the Special Issue Polymers and Ionic Liquids: Shaping up a New Generation of High Performances Nanomaterials)

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11 pages, 1777 KiB

Open AccessArticle

Construction of Novel Polymerizable Ionic Liquid Microemulsions and the In Situ Synthesis of Poly(Ionic Liquid) Adsorbents

by Aili Wang, Shuhui Li, Hou Chen, Ying Liu and Xiong Peng

Nanomaterials 2019, 9(3), 454; https://doi.org/10.3390/nano9030454 - 18 Mar 2019

Cited by 15 | Viewed by 3217

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

(This article belongs to the Special Issue Polymers and Ionic Liquids: Shaping up a New Generation of High Performances Nanomaterials)

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9 pages, 5493 KiB

Open AccessArticle

Investigation on the Crystallization Behaviors of Polyoxymethylene with a Small Amount of Ionic Liquid

by Qi Jiao, Qin Chen, Lian Wang, Hualin Chen and Yongjin Li

Nanomaterials 2019, 9(2), 206; https://doi.org/10.3390/nano9020206 - 05 Feb 2019

Cited by 16 | Viewed by 3004

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

(This article belongs to the Special Issue Polymers and Ionic Liquids: Shaping up a New Generation of High Performances Nanomaterials)

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17 pages, 4504 KiB

Open AccessArticle

Gelled Electrolyte Containing Phosphonium Ionic Liquids for Lithium-Ion Batteries

by Mélody Leclère, Laurent Bernard, Sébastien Livi, Michel Bardet, Armel Guillermo, Lionel Picard and Jannick Duchet-Rumeau

Nanomaterials 2018, 8(6), 435; https://doi.org/10.3390/nano8060435 - 14 Jun 2018

Cited by 17 | Viewed by 4636

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

(This article belongs to the Special Issue Polymers and Ionic Liquids: Shaping up a New Generation of High Performances Nanomaterials)

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Review

Jump to: Research

26 pages, 3281 KiB

Open AccessReview

New Developments in Material Preparation Using a Combination of Ionic Liquids and Microwave Irradiation

by Yannan Wang, Qidong Hou, Meiting Ju and Weizun Li

Nanomaterials 2019, 9(4), 647; https://doi.org/10.3390/nano9040647 - 22 Apr 2019

Cited by 28 | Viewed by 5933

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

(This article belongs to the Special Issue Polymers and Ionic Liquids: Shaping up a New Generation of High Performances Nanomaterials)

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