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17 pages, 3836 KiB

Open AccessArticle

Thermally Switchable Electrically Conductive Thermoset rGO/PK Self-Healing Composites

by Esteban Araya-Hermosilla, Alice Giannetti, Guilherme Macedo R. Lima, Felipe Orozco, Francesco Picchioni, Virgilio Mattoli, Ranjita K. Bose and Andrea Pucci

Polymers 2021, 13(3), 339; https://doi.org/10.3390/polym13030339 - 21 Jan 2021

Cited by 15 | Viewed by 3239

Abstract

Among smart materials, self-healing is one of the most studied properties. A self-healing polymer can repair the cracks that occurred in the structure of the material. Polyketones, which are high-performance thermoplastic polymers, are a suitable material for a self-healing mechanism: a furanic pendant [...] Read more.

Among smart materials, self-healing is one of the most studied properties. A self-healing polymer can repair the cracks that occurred in the structure of the material. Polyketones, which are high-performance thermoplastic polymers, are a suitable material for a self-healing mechanism: a furanic pendant moiety can be introduced into the backbone and used as a diene for a temperature reversible Diels-Alder reaction with bismaleimide. The Diels-Alder adduct is formed at around 50 °C and broken at about 120 °C, giving an intrinsic, stimuli-responsive self-healing material triggered by temperature variations. Also, reduced graphene oxide (rGO) is added to the polymer matrix (1.6–7 wt%), giving a reversible OFF-ON electrically conductive polymer network. Remarkably, the electrical conductivity is activated when reaching temperatures higher than 100 °C, thus suggesting applications as electronic switches based on self-healing soft devices. Full article

(This article belongs to the Special Issue Recent Advances in Self-Healing Polymers)

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18 pages, 5779 KiB

Open AccessArticle

3D Printing of a Self-Healing Thermoplastic Polyurethane through FDM: From Polymer Slab to Mechanical Assessment

by Linda Ritzen, Vincenzo Montano and Santiago J. Garcia

Polymers 2021, 13(2), 305; https://doi.org/10.3390/polym13020305 - 19 Jan 2021

Cited by 23 | Viewed by 6077

Abstract

The use of self-healing (SH) polymers to make 3D-printed polymeric parts offers the potential to increase the quality of 3D-printed parts and to increase their durability and damage tolerance due to their (on-demand) dynamic nature. Nevertheless, 3D-printing of such dynamic polymers is not [...] Read more.

The use of self-healing (SH) polymers to make 3D-printed polymeric parts offers the potential to increase the quality of 3D-printed parts and to increase their durability and damage tolerance due to their (on-demand) dynamic nature. Nevertheless, 3D-printing of such dynamic polymers is not a straightforward process due to their polymer architecture and rheological complexity and the limited quantities produced at lab-scale. This limits the exploration of the full potential of self-healing polymers. In this paper, we present the complete process for fused deposition modelling of a room temperature self-healing polyurethane. Starting from the synthesis and polymer slab manufacturing, we processed the polymer into a continuous filament and 3D printed parts. For the characterization of the 3D printed parts, we used a compression cut test, which proved useful when limited amount of material is available. The test was able to quasi-quantitatively assess both bulk and 3D printed samples and their self-healing behavior. The mechanical and healing behavior of the 3D printed self-healing polyurethane was highly similar to that of the bulk SH polymer. This indicates that the self-healing property of the polymer was retained even after multiple processing steps and printing. Compared to a commercial 3D-printing thermoplastic polyurethane, the self-healing polymer displayed a smaller mechanical dependency on the printing conditions with the added value of healing cuts at room temperature. Full article

(This article belongs to the Special Issue Recent Advances in Self-Healing Polymers)

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14 pages, 28340 KiB

Open AccessArticle

Mechanical Properties of Poly(ethylene-co-methacrylic acid) Reinforced with Carbon Fibers

by Tatjana Haramina, Daniel Pugar, Darko Ivančević and Ivica Smojver

Polymers 2021, 13(1), 165; https://doi.org/10.3390/polym13010165 - 5 Jan 2021

Cited by 5 | Viewed by 3187

Abstract

The capability of poly(ethylene-co-methacrylic acid) (E/MAA) to self-heal is well known, however, its mechanical properties are weak. In this study, composites with single and double layers of unidirectional (UD) carbon fibers were prepared by compression molding. Even a low mass fraction of fibers [...] Read more.

The capability of poly(ethylene-co-methacrylic acid) (E/MAA) to self-heal is well known, however, its mechanical properties are weak. In this study, composites with single and double layers of unidirectional (UD) carbon fibers were prepared by compression molding. Even a low mass fraction of fibers substantially improved the polymer. The flexural and tensile properties were tested at 0°, 45° and 90° fibers direction and compared to those of the matrix. The mechanical properties in the 0° direction proved superior. Flexural properties depended on the reinforcement distance from the stress neutral plane. The tensile modulus in the 0° direction was 13 times greater despite only a 2.5% mass fraction of fibers. However, both tensile modulus and strength were observed to degrade in the 90° direction. Dynamic mechanical analysis showed the dependence of both structure and properties on the thermal history of E/MAA. Tensile tests after ballistic impact showed that the modulus of the self-healed E/MAA was not affected, yet the strength, yield point, and particularly the elongation at break were reduced. A composite with higher fiber content could be prepared by mixing milled E/MAA particles in fibers prior to compression. Full article

(This article belongs to the Special Issue Recent Advances in Self-Healing Polymers)

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22 pages, 6479 KiB

Open AccessArticle

Alleviating Molecular-Scale Damages in Silica-Reinforced Natural Rubber Compounds by a Self-Healing Modifier

by Bashir Algaily, Wisut Kaewsakul, Siti Salina Sarkawi and Ekwipoo Kalkornsurapranee

Polymers 2021, 13(1), 39; https://doi.org/10.3390/polym13010039 - 24 Dec 2020

Cited by 7 | Viewed by 3255

Abstract

The property retentions of silica-reinforced natural rubber vulcanizates with various contents of a self-healing modifier called EMZ, which is based on epoxidized natural rubber (ENR) modified with hydrolyzed maleic anhydride (HMA) as an ester crosslinking agent plus zinc acetate dihydrate (ZAD) as a [...] Read more.

The property retentions of silica-reinforced natural rubber vulcanizates with various contents of a self-healing modifier called EMZ, which is based on epoxidized natural rubber (ENR) modified with hydrolyzed maleic anhydride (HMA) as an ester crosslinking agent plus zinc acetate dihydrate (ZAD) as a transesterification catalyst, were investigated. To validate its self-healing efficiency, the molecular-scale damages were introduced to vulcanizates using a tensile stress–strain cyclic test following the Mullins effect concept. The processing characteristics, reinforcing indicators, and physicomechanical and viscoelastic properties of the compounds were evaluated to identify the influences of plausible interactions in the system. Overall results demonstrate that the property retentions are significantly enhanced with increasing EMZ content at elevated treatment temperatures, because the EMZ modifier potentially contributes to reversible linkages leading to the intermolecular reparation of rubber network. Furthermore, a thermally annealing treatment of the damaged vulcanizates at a high temperature, e.g., 120 °C, substantially enhances the property recovery degree, most likely due to an impact of the transesterification reaction of the ester crosslinks adjacent to the molecular damages. This reaction can enable bond interchanges of the ester crosslinks, resulting in the feasibly exchanged positions of the ester crosslinks between the broken rubber molecules and, thus, achievable self-reparation of the damages. Full article

(This article belongs to the Special Issue Recent Advances in Self-Healing Polymers)

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13 pages, 5249 KiB

Open AccessArticle

Effect of Microcapsule Content on Diels-Alder Room Temperature Self-Healing Thermosets

by Sadella C. Santos, John J. La Scala and Giuseppe R. Palmese

Polymers 2020, 12(12), 3064; https://doi.org/10.3390/polym12123064 - 21 Dec 2020

Cited by 3 | Viewed by 2011

Abstract

A furan functionalized epoxy-amine thermoset with an embedded microcapsule healing system that utilizes reversible Diels-Alder healing chemistry was used to investigate the influence of microcapsule loading on healing efficiency. A urea-formaldehyde encapsulation technique was used to create capsules with an average diameter of [...] Read more.

A furan functionalized epoxy-amine thermoset with an embedded microcapsule healing system that utilizes reversible Diels-Alder healing chemistry was used to investigate the influence of microcapsule loading on healing efficiency. A urea-formaldehyde encapsulation technique was used to create capsules with an average diameter of 150 µm that were filled with a reactive solution of bismaleimide in phenyl acetate. It was found that optimum healing of the thermoset occurred at 10 wt% microcapsule content for the compositions investigated. The diffusion of solvent through the crack interface and within fractured samples was investigated using analytical diffusion models. The decrease in healing efficiency at higher microcapsule loading was attributed partially to solvent-induced plasticization at the interface. The diffusion analysis also showed that the 10% optimum microcapsule concentration occurs for systems with the same interfacial solvent concentration. This suggests that additional physical and chemical phenomena are also responsible for the observed optimum. Such phenomena could include a reduction in surface area available for healing and the saturation of interfacial furan moieties by reaction with increasing amounts of maleimide. Both would result from increased microcapsule loading. Full article

(This article belongs to the Special Issue Recent Advances in Self-Healing Polymers)

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24 pages, 4696 KiB

Open AccessArticle

Self-Healing in Mobility-Restricted Conditions Maintaining Mechanical Robustness: Furan–Maleimide Diels–Alder Cycloadditions in Polymer Networks for Ambient Applications

by Dorothee Ehrhardt, Jessica Mangialetto, Jolien Bertouille, Kurt Van Durme, Bruno Van Mele and Niko Van den Brande

Polymers 2020, 12(11), 2543; https://doi.org/10.3390/polym12112543 - 30 Oct 2020

Cited by 21 | Viewed by 4060

Abstract

Two reversible polymer networks, based on Diels–Alder cycloadditions, are selected to discuss the opportunities of mobility-controlled self-healing in ambient conditions for which information is lacking in literature. The main methods for this study are (modulated temperature) differential scanning calorimetry, microcalorimetry, dynamic rheometry, dynamic [...] Read more.

Two reversible polymer networks, based on Diels–Alder cycloadditions, are selected to discuss the opportunities of mobility-controlled self-healing in ambient conditions for which information is lacking in literature. The main methods for this study are (modulated temperature) differential scanning calorimetry, microcalorimetry, dynamic rheometry, dynamic mechanical analysis, and kinetic simulations. The reversible network 3M-3F630 is chosen to study the conceptual aspects of diffusion-controlled Diels–Alder reactions from 20 to 65 °C. Network formation by gelation is proven and above 30 °C gelled glasses are formed, while cure below 30 °C gives ungelled glasses. The slow progress of Diels–Alder reactions in mobility-restricted conditions is proven by the further increase of the system’s glass transition temperature by 24 °C beyond the cure temperature of 20 °C. These findings are employed in the reversible network 3M-F375PMA, which is UV-polymerized, starting from a Diels–Alder methacrylate pre-polymer. Self-healing of microcracks in diffusion-controlled conditions is demonstrated at 20 °C. De-gelation measurements show the structural integrity of both networks up to at least 150 °C. Moreover, mechanical robustness in 3M-F375PMA is maintained by the poly(methacrylate) chains to at least 120 °C. The self-healing capacity is simulated in an ambient temperature window between −40 and 85 °C, supporting its applicability as self-healing encapsulant in photovoltaics. Full article

(This article belongs to the Special Issue Recent Advances in Self-Healing Polymers)

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Review

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22 pages, 5166 KiB

Open AccessReview

Self-Healing Polymer Nanocomposite Materials by Joule Effect

by Jaime Orellana, Ignacio Moreno-Villoslada, Ranjita K. Bose, Francesco Picchioni, Mario E. Flores and Rodrigo Araya-Hermosilla

Polymers 2021, 13(4), 649; https://doi.org/10.3390/polym13040649 - 22 Feb 2021

Cited by 36 | Viewed by 6218

Abstract

Nowadays, the self-healing approach in materials science mainly relies on functionalized polymers used as matrices in nanocomposites. Through different physicochemical pathways and stimuli, these materials can undergo self-repairing mechanisms that represent a great advantage to prolonging materials service-life, thus avoiding early disposal. Particularly, [...] Read more.

Nowadays, the self-healing approach in materials science mainly relies on functionalized polymers used as matrices in nanocomposites. Through different physicochemical pathways and stimuli, these materials can undergo self-repairing mechanisms that represent a great advantage to prolonging materials service-life, thus avoiding early disposal. Particularly, the use of the Joule effect as an external stimulus for self-healing in conductive nanocomposites is under-reported in the literature. However, it is of particular importance because it incorporates nanofillers with tunable features thus producing multifunctional materials. The aim of this review is the comprehensive analysis of conductive polymer nanocomposites presenting reversible dynamic bonds and their energetical activation to perform self-healing through the Joule effect. Full article

(This article belongs to the Special Issue Recent Advances in Self-Healing Polymers)

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32 pages, 2659 KiB

Open AccessReview

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

by Stefano Paolillo, Ranjita K. Bose, Marianella Hernández Santana and Antonio M. Grande

Polymers 2021, 13(2), 201; https://doi.org/10.3390/polym13020201 - 8 Jan 2021

Cited by 68 | Viewed by 8115

Abstract

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 [...] Read more.

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. Full article

(This article belongs to the Special Issue Recent Advances in Self-Healing Polymers)

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