Open access peer-reviewed chapter

Thermoreversible Polymeric Nanocomposites

Written By

Ranjita K. Bose, Francesco Picchioni and Henky Muljana

Submitted: March 8th, 2018 Reviewed: July 10th, 2018 Published: November 5th, 2018

DOI: 10.5772/intechopen.80218

Chapter metrics overview

967 Chapter Downloads

View Full Metrics

Abstract

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.

Keywords

  • nanocomposites
  • thermally reversible interactions
  • Diels-Alder
  • graphene
  • carbon nanotubes

1. Introduction

Polymeric composites are all around us. The addition of nanofillers to polymers has opened pathways for designing materials with improved functionalities. The synergistic effects of each component can result in better mechanical properties, thermal or electrical conductivity, and enhanced optical properties. The wide range of applications, spanning diverse fields such as civil engineering (building and constructions), electronics, biomedical materials, etc., renders this kind of materials essential for our daily life. The simplest structure of a composite is the one consisting of a polymeric matrix in which a solid filler is dispersed. The logic behind this combination is the ability to manipulate the composite properties as function of those of the individual components and the interfacial bonding [1]. However, even at this very simple level, the system can be considered as quite complex. In particular, the geometrical shape of the filler as fibers, platelets, and particles (respectively approached as 1-, 2-, and 3-dimensional objects) is pivotal in determining the final properties. Many studies have been dedicated in the past to understand these features and to develop physical models that are able to predict the properties as a function of the structure [2, 3, 4, 5, 6, 7, 8].

One of the challenges in nanocomposites is the nanoscale dispersion and distribution of the filler, which can be achieved by chemical modification of the filler surface. During the last three decades, many works have been focusing on a relatively novel concept, i.e., on the use of a covalent, yet thermally reversible, linkage between the filler and the matrix. On the one hand, this fits the general idea that (thermally) reversible linkages between the components could significantly improve some mechanical characteristics, such as impact properties. This can be achieved also by using relatively weaker interaction forces, such as hydrogen bonding. On the other hand, the use of covalent, and yet reversible bonds, might significantly help in achieving the same goal while avoiding any significant compromise on the strength of the final material [9, 10]. Indeed, among all possible thermoreversible interactions, only covalent bonds can be defined as relatively strong (more than a few kcal/mol) and metal free (Figure 1).

Figure 1.

Schematic representation of different kinds of thermally reversible interactions.

Hydrogen bonding [11, 12, 13, 14] and ionic interactions [9] have been often used as thermally reversible interactions for composites of different kinds. One of the main driving forces behind the use of such a strategy is the presence of special end properties. For example, the dynamic nature of thermally reversible interactions (as a function of temperature) endows composites with self-healing behavior [11, 13, 15, 16, 17] and shape-memory characteristics [18, 19]. Furthermore, the same kind of reversible chemistry can be also applied in solution [20, 21, 22] where the crosslinking yields gels of different nature finding applications in very popular fields such as biomedical products. It must also be stressed that very recently particular attention has been paid to a new research field, still in its infancy, dealing with the use of supramolecular polymer in composites [23, 24]. The overall concept, stemming from the use of reversible interaction for the polymer backbone, nicely fits in the thermally reversible context although with even more remarkable loss of properties at relatively high temperatures. In the present chapter, we focus on the use of the Diels-Alder (DA) reaction as a modification toolbox for nanocomposites. While presenting a general overview of the recent literature, we aim to highlight the strategic chemical modification routes and, whenever possible, the added value of such strategy for the properties of the final composite. Other kinds of “click” reactions are also possible, the reader being referred to recent works in the field [25].

Advertisement

2. Chemical strategies for the insertion of DA groups in nanocomposites

The use of Diels-Alder chemistry as a modification tool for composite materials stems from the peculiar characteristics of this reaction. The choice to proceed with or without catalyst at relatively mild temperatures as well as the intimate connection between the forward (DA) and reverse, i.e., retro Diels-Alder (rDA) reactions and the structure of the diene and dienophile render this reaction ideal in terms of being able to control its decrosslinking as a function of temperature. As a consequence, many efforts have been reported in the use of DA to decorate various types of fillers including carbon nanotubes (CNT) [20, 26] and silica [27, 28]. In particular, CNT represent a popular choice (Figure 2) in view of their increasing availability and the kaleidoscopic variety of properties they potentially endow the composite with (electrical conductivity, strength, and shape memory).

Figure 2.

Schematic overview of CNT decoration via the DA reaction. Adapted and redrawn based on [29,30,31,32].

Functionalization of CNT improves their dispersion in polymer matrices and also improves the processability of the nanocomposites. The DA reaction has a clear effect on the debundling of CNT [29] and also on their dispersion in polymeric matrixes [33]. The mechanical property enhancement is due to two mechanisms: the fillers act as (additional) crosslink points while also serving as stress-transfer points, distributing the stress to the polymer matrix uniformly. In both cases, the key feature is the improved adhesion at the interface between filler and matrix [34]. It is also noteworthy how CNT can act as both diene and dienophile in the DA reaction, respectively, with maleimide and furan groups [30]. As these reactions are mainly aimed at introducing functional groups on the CNT surface, this testifies the versatility of the approach even if in some cases side reactions might be present [19] and there is no mention of the reversibility or its use [31]. Some of the reported approaches towards incorporation of CNT via DA clearly indicate relatively easy synthetic routes [35] (Figure 3).

Figure 3.

Simple incorporation of CNT into epoxy-like resin [35].

In the present case, functionalized CNT and furfuryl amine are simply mixed with di-glycidyl-bisphenol A, yielding in one step, a multifunctional monomer that can be subsequently crosslinked via addition of a bis-maleimide. In this case, the self-healing behavior can be induced by near-infrared (NIR) irradiation (Figure 4). Scratch healing was demonstrated in the vicinity of the damage using optical microscopy by optimizing the location and power of the laser source. The presence of the CNT ensured the overall robustness and integrity of the nanocomposite samples while also increasing the photothermal conversion efficiency, which enhanced self-healing.

Figure 4.

NIR induced self-healing process of epoxy resins [35].

CNT-polymer nanocomposites were demonstrated as reversibly bendable actuators in solvent detection sensors [34]. The incorporation of CNT was crucial in this work as they contributed toward the thermal and electrical conductivity necessary for this particular application. The reversible DA linkages comprising of furan and maleimide moieties ensured good adhesion between the dissimilar layers in the bilayer sensors. This concept of anisotropic expansion in different environments could be extended to multiresponsive materials with applications in soft robotics or self-deployable actuators in different stimuli such as moisture, solvents, pH, and/or temperature. Moreover, the incorporation at the same time of CNT with magnetic nanoparticles (Figure 5) is also possible via the DA approach [36].

Figure 5.

Preparation of composites based on CNT and magnetic particles [36,37].

In this case, the functionalization of Fe3O4 nanoparticles with maleimide groups is followed (route A) by DA reaction with CNT and finally by mixing with the polymeric matrix. In another approach [37] (route B), the functionalized nanoparticles can be directly embedded in a telechelic polymer via the DA reaction, thus yielding composites without CNT but with magnetic particles. The simplicity of these approaches is in stark contrast with the complex behavior, particularly the response to heat, electricity, and magnetic field. It is worth also noticing, for electrospun fibers produced in this way, the relevant toughening behavior, which might indeed be related to the thermally reversible interaction at the interface.

The extreme precision of the DA reaction, almost devoid of any side reaction, renders it particularly suitable also for simple decoration of different fillers. A recent example [38] is constituted by the synthesis of nanocomposites, forming gold particles and poly-p-phenylene ethynylene (Figure 6).

Figure 6.

Maleimide functionalized gold (MA-Au)-nanoparticles-based composite [38].

As expected, the good adhesion at the interface has a clear influence on the self-assembly behavior of the Au-nanoparticles, and peculiarly in this case, this improves the electronic communication between the conducting backbone and the nanoparticles. Other kinds of nanoparticles, with tailor-made structure and properties, have also been reported, particularly aiming at producing high-k nanocomposites for applications as motion sensors [39]. In this case, the dielectrical permittivity of the material is tunable as a function of the filler intake and can be systematically recovered upon self-healing of the corresponding films. The hybrid polymer-ceramic materials had an improved dielectric property and improved retention of capacitance due to the recoverable DA bonds. The specific capacitance was shown to restore up to 82% even after 10 cycles of cutting and healing. Thus, in addition to improved interfacial properties, the DA reaction also enables the lifetime extension of such materials during application. Functionalized nanoparticles (with DA groups) might have an important role as additives as they have been also employed as dynamic crosslinker in gels [40].

The same approach has been used for POSS-based composites [41] and polyesters (Figure 7). The partially crosslinked network was insoluble to common organic solvents while showing thermoreversibility at 120°C. The occurrence of the DA reaction between furan and maleimide functional groups was induced by melt mixing as opposed to casting. The resultant nanocomposites had significantly higher flexural and tensile moduli as well as glass transition temperature as compared to the polymer matrix. This mechanical behavior clearly highlights the dynamic nature of the bonds, while at the same time suggesting a synergy in terms of strength and impact properties.

Figure 7.

POSS-based composites [41].

Besides CNT and nanoparticles, graphene has also attracted much attention. This is not surprising when making allowances for the similar structure and reactivity of these two fillers. In one report, self-healing was achieved by catalyst containing microcapsules and graphene was added to offset the reduction in tensile strength due to the addition of the weaker microcapsules [42]. Graphene-based nanocomposites have been reported for possible application as supercapacitors [43]. In this case, a conductive polymer polypyrrole was chosen due to its stability upon exposure to oxygen, cheap cost, and easy synthesis. Tetrazine derivatives were reacted onto reduced graphene sheets via the inverse electron demand Diels-Alder reaction. The nanocomposites showed good electrochemical properties and a small resistance due to easy ion accessibility and thus are promising as potential electrode materials for supercapacitors. Graphene-based nanocomposites have also been demonstrated as strain sensors for flexible electronics [44]. Here, furfuryl containing polyurethane was crosslinked with a bis-maleimide onto reduced functionalized graphene oxide sheets. The nanocomposites showed good flexibility, and thermal and electrical conductivity was required for the aforementioned application. Healing via rDA reaction was achieved by microwave heating in <5 min. A particularly simple approach (Figure 8) allows easy fabrication of composites based on graphene and a multifunctional DA crosslinker [45].

Figure 8.

Nanocomposite fabrication via DA reaction between graphene and a multifunctional crosslinker.

The mechanical behavior of the final product clearly reflects the pivotal role of the graphene intake (Figure 9). As expected, tensile strength and Young’s modulus increase with the graphene intake while the elongation at break decreases.

Figure 9.

Mechanical properties of nanocomposites as function of the graphene intake [45].

Although in a different work [46], a significant improvement of the impact properties has also been reported and preliminarily attributed to the wave propagation through the graphene platelets. Also in the case of graphene, as for CNT, reactivity as diene or dienophile, can be exploited [47]. The occurrence of the reaction between graphene and the maleimide crosslinker is once more testified by the excellent dispersion of the graphene sheets within the matrix. These sheets act as a local thermal collector by converting adsorbed infrared or microwave energy into heat, thus triggering the reversible bond behavior. This renders the final composite responsive to multiple stimuli (heat, electricity, infrared, microwave) for self-healing and shape memory. These effects are then on top of the change in mechanical properties as, for example, highlighted above. Such improvement of mechanical behavior can also be “dramatic” as reported in the case of styrene-butadiene rubber (SBR) functionalized with furan groups, mixed with furan-functionalized CNT and crosslinked by addition of a bis-maleimide [48]. In this case, a relevant increase (over 200%) in modulus values and toughness could be booked. This highlights once more the synergy in the combination of nanofillers and their thermally reversible adhesion to the matrix. The concept of “local” self-healing, for which nanoparticles play a crucial role, is actually broader than merely graphene and DA. The fact that heat can be generated locally renders the crosslinking kinetics faster [49] also in the case of ionic interactions and magnetic nanoparticles.

In addition to relatively novel nanofillers, composites with thermally reversible interactions have also been prepared based on more “classical” ones, such as silica [50] again with the general aim of inducing self-healing behavior. The general preparation strategy is similar to the ones presented above and entails the functionalization of the polymer and the filler with furan groups, followed by crosslinking with bis-maleimides [50]. However, in the special case of silica, also different approaches are possible in view of the possibility to obtain silica as result of sol-gel reactions (Figure 10).

Figure 10.

Sol-gel approach toward the synthesis of silica-based thermally reversible composites [50].

Furan and maleimide groups are the most commonly used diene and dienophile in self-healing reversible systems. This is due to their high reactivity and low activation energy of the rDA reaction, which enables the rDA reaction to proceed around 100 to 140°C. In the majority of the examples illustrated so far, attention has been paid to the occurrence of the DA reaction while aiming at relatively low rDA temperature (typically 120°C) in view of self-healing properties at relatively mild experimental conditions. In some cases, a catalyst has also been used to achieve self-healing at even lower temperatures [51]. On the other hand, for some specific applications in extreme environments (e.g., in automotive or aerospace), thermal stability up to 200°C is a conditio sine qua non. This can be achieved by changing the chemical structure of the DA groups. A recent example involves the use of anthracene and maleimide groups [52] (Figure 11).

Figure 11.

Anthracene-based composites [52].

The resulting polyurethanes (PU) show self-healing behavior by pure DA reaction for mechanically cleaved adducts. The use of continuous fibers also helped with mechanical robustness comparable to those of engineering polymers and structural composites. These materials were exceptionally thermally stable and showed high strength, stiffness, and toughness.

Advertisement

3. Future outlook

Thermal reversibility allows adding another tool for the design of smart composites. Properties such as self-healing and shape memory, besides the “classical effects” on thermal and mechanical ones, are easily added to the composite behavior. The sensitivity to multiple external stimuli such as electricity, irradiation, and heat [11, 18, 53, 54], represents a focal point for the design of smart materials. An added value in this case is the possibility (via irradiation) of remote-induced self-healing as well as of ultrafast kinetics [55]. In this context, it is conceivable that many research efforts will be spent in achieving a systematic control over this multifunctionality and responsiveness. In turn, this will require even more precise control over the kind of functional groups present and the chemical structure in more general terms. Further studies are then envisioned in the general field of structure-property relationships, for example, by a systematic investigation on the influence of spacers [56] on the DA decrosslinking. Other factors influencing the structure of the composite and thus its properties, such as the nature of the filler and the backbone, continue to represent points of attention. The possibility to extend the concept to inorganic polymers [57], the use of fullerene derivatives [58] as well the general trend toward the use of green fillers [59] have been recently reported, but deserve further study in order to explore all possible application fields. Finally, the combination of the properties highlighted above and their synergy with additional ones, such as color change upon thermally reversible behavior [60], constitute attractive characteristics of these materials.

Advertisement

Conflict of interest

The authors declare no conflict of interests,

References

  1. 1. Lin H, Liu Y. Reactive hybrid of polyhedral oligomeric silsesquioxane (POSS) and sulfur as a building block for self-healing materials. Macromolecular Rapid Communications. 2017;38(10):1700051. DOI: 10.1002/marc.201700051
  2. 2. Bostanabad R, Zhang Y, Li X, Kearney T, Brinson LC, Apley DW, et al. Computational microstructure characterization and reconstruction: Review of the state-of-the-art techniques. Progress in Materials Science. 2018;95:1-41. DOI: 10.1016/j.pmatsci.2018.01.005
  3. 3. Myshkin N, Kovalev A. Adhesion and surface forces in polymer tribology-a review. Friction. 2018;6(2):143-155. DOI: 10.1007/s40544-018-0203-0
  4. 4. Xiong X, Shen SZ, Hua L, Liu JZ, Li X, Wan X, et al. Finite element models of natural fibers and their composites: A review. Journal of Reinforced Plastics and Composites. 2018;37(9):617-635. DOI: 10.1177/0731684418755552
  5. 5. Boris D, Xavier L, Damien S. The tensile behaviour of biaxial and triaxial braided fabrics. Journal of Industrial Textiles. 2018;47(8):2184-2204. DOI: 10.1177/1528083716654469
  6. 6. Bogenfeld R, Kreikemeier J, Wille T. Review and benchmark study on the analysis of low-velocity impact on composite laminates. Engineering Failure Analysis. 2018;86:72-99. DOI: 10.1016/j.engfailanal.2017.12.019
  7. 7. Hunter A, Leu B, Beyerlein IJ. A review of slip transfer: Applications of mesoscale techniques. Journal of Materials Science. 2018;53(8):5584-5603. DOI: 10.1007/s10853-017-1844-5
  8. 8. Li N, Liu X. Review: Mechanical behavior of metal/ceramic interfaces in nanolayered composites-experiments and modeling. Journal of Materials Science. 2018;53(8):5562-5583. DOI: 10.1007/s10853-017-1767-1
  9. 9. Potier F, Guinault A, Delalande S, Sanchez C, Ribot F, Rozes L. Nano-building block based-hybrid organic-inorganic copolymers with self-healing properties. Polymer Chemistry. 2014;5(15):4474-4479. DOI: 10.1039/c4py00172a
  10. 10. Amaral AJR, Emamzadeh M, Pasparakis G. Transiently malleable multi-healable hydrogel nanocomposites based on responsive boronic acid copolymers. Polymer Chemistry. 2018;9(4):525-537. DOI: 10.1039/c7py01202k
  11. 11. Zhu B, Noack M, Merindol R, Barner-Kowollik C, Walther A. Light-adaptive supramolecular nacre-mimetic nanocomposites. Nano Letters. 2016;16(8):5176-5182. DOI: 10.1021/acs.nanolett.6b02127
  12. 12. Xing L, Li Q, Zhang G, Zhang X, Liu F, Liu L, et al. Self-healable polymer nanocomposites capable of simultaneously recovering multiple functionalities. Advanced Functional Materials. 2016;26(20):3524-3531. DOI: 10.1002/adfm.201505305
  13. 13. Noack M, Merindol R, Zhu B, Benitez A, Hackelbusch S, Beckert F, et al. Light-fueled, spatiotemporal modulation of mechanical properties and rapid self-healing of graphene-doped supramolecular elastomers. Advanced Functional Materials. 2017;27(25):1700767. DOI: 10.1002/adfm.201700767
  14. 14. Yari H, Mohseni M, Messori M. A scratch resistant yet healable automotive clearcoat containing hyperbranched polymer and POSS nanostructures. RSC Advances. 2016;6(79):76028-76041. DOI: 10.1039/c6ra07824a
  15. 15. Duarah R, Karak N. High performing smart hyperbranched polyurethane nanocomposites with efficient self-healing, self-cleaning and photocatalytic attributes. New Journal of Chemistry. 2018;42(3):2167-2179. DOI: 10.1039/c7nj03889e
  16. 16. Li Y, Gao F, Xue Z, Luan Y, Yan X, Guo Z, et al. Synergistic effect of different graphene-CNT heterostructures on mechanical and self-healing properties of thermoplastic polyurethane composites. Materials and Design. 2018;137:438-445. DOI: 10.1016/j.matdes.2017.10.018
  17. 17. Moazzen K, Zohuriaan-Mehr MJ, Jahanmardi R, Kabiri K. Toward poly(furfuryl alcohol) applications diversification: Novel self-healing network and toughening epoxy-novolac resin. Journal of Applied Polymer Science. 2018;135(12):45921. DOI: 10.1002/app.45921
  18. 18. Bai J, Shi Z. Dynamically cross-linked elastomer hybrids with light-induced rapid and efficient self-healing ability and reprogrammable shape memory behavior. ACS Applied Materials & Interfaces. 2017;9(32):27213-27222. DOI: 10.1021/acsami.7b06407
  19. 19. Chuo T, Liu Y. Preparation of self-healing organic-inorganic nanocomposites with the reactions between methacrylated polyhedral oligomeric silsesquioxanes and furfurylamine. Composites Science and Technology. 2015;118:236-243. DOI: 10.1016/j.compscitech.2015.09.005
  20. 20. Garcia-Garcia JM, Mar Bernal M, Verdejo R, Lopez-Manchado MA, Doncel-Perez E, Garrido L, et al. Semiconductive bionanocomposites of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and MWCNTs for neural growth applications. Journal of Polymer Science Part B-Polymer Physics. 2014;52(5):349-360. DOI: 10.1002/polb.23417
  21. 21. Garcia-Astrain C, Ahmed I, Kendziora D, Guaresti O, Eceiza A, Fruk L, et al. Effect of maleimide-functionalized gold nanoparticles on hybrid biohydrogels properties. RSC Advances. 2015;5(62):50268-50277. DOI: 10.1039/c5ra06806a
  22. 22. Garcia-Astrain C, Miljevic M, Ahmed I, Martin L, Eceiza A, Fruk L, et al. Designing hydrogel nanocomposites using TiO2 as clickable cross-linkers. Journal of Materials Science. 2016;51(11):5073-5081. DOI: 10.1007/s10853-016-9810-1
  23. 23. de Espinosa LM, Fiore GL, Weder C, Foster EJ, Simon YC. Healable supramolecular polymer solids. Progress in Polymer Science. 2015;49-50:60-78. DOI: 10.1016/j.pro-gpolymsci.2015.04.003
  24. 24. Zhu B, Merindol R, Benitez AJ, Wang B, Walther A. Supramolecular engineering of hierarchically self-assembled, bioinspired, cholesteric nanocomposites formed by cellulose nanocrystals and polymers. ACS Applied Materials & Interfaces. 2016;8(17):11031-11040. DOI: 10.1021/acsami.6b00410
  25. 25. Arslan M, Tasdelen MA. Polymer nanocomposites via click chemistry reactions. Polymer. 2017;9(10):499. DOI: 10.3390/polym9100499
  26. 26. Kaur A, Singh I, Kumar J, Bhatnagar C, Dixit SK, Bhatnagar PK, et al. Enhancement in the performance of multi-walled carbon nanotube: Poly(methylmethacrylate) composite thin film ethanol sensors through appropriate nanotube functionalization. Materials Science in Semiconductor Processing. 2015;31:166-174. DOI: 10.1016/j.mssp.2014.11.030
  27. 27. Ursache O, Gaina V, Gaina C. Poly(vinyl alcohol)-inorganic hybrid materials with Thermocleavable groups. Polymer - Plastics Technology and Engineering. 2013;52(6):546-552. DOI: 10.1080/03602559.2012.762377
  28. 28. Engel T, Kickelbick G. Thermoreversible reactions on inorganic nanoparticle surfaces: Diels-Alder reactions on sterically crowded surfaces. Chemistry of Materials. 2013;25(2):149-157. DOI: 10.1021/cm303049k
  29. 29. Hayden H, Gun'ko YK, Perova T, Grudinkin S, Moore A, Obraztsova ED. Investigation of tetrazine functionalised single walled carbon nanotubes. Plastics, Rubber and Composites. 2009;38(6):253-256. DOI: 10.1179/174328909X435384
  30. 30. Munirasu S, Albuerne J, Boschetti-de-Fierro A, Abetz V. Functionalization of carbon materials using the Diels-Alder reaction. Macromolecular Rapid Communications. 2010;31(6):574-579. DOI: 10.1002/marc.200900751
  31. 31. Zhang W, Zhou Z, Li Q, Chen G. Controlled dielectric properties of polymer composites from coating multiwalled carbon nanotubes with octa-acrylate silsesquioxane through Diels-Alder cycloaddition and atom transfer radical polymerization. Industrial and Engineering Chemistry Research. 2014;53(16):6699-6707. DOI: 10.1021/ie404204g
  32. 32. Wang Y, Chang C, Liu Y. Benzoxazine-functionalized multi-walled carbon nanotubes for preparation of electrically-conductive polybenzoxazines. Polymer. 2012;53(1):106-112. DOI: 10.1016/j.polymer.2011.11.040
  33. 33. Lin C, Sheng D, Liu X, Xu S, Ji F, Dong L, et al. Polymer. 2017;127:241-250. DOI: 10.1016/j.polymer.2017.09.001
  34. 34. Toncheva A, Willocq B, Khelifa F, Douheret O, Lambert P, Dubois P, et al. Bilayer solvent and vapor-triggered actuators made of cross-linked polymer architectures via Diels-Alder pathways. Journal of Materials Chemistry B. 2017;5(28):5556-5563. DOI: 10.1039/c7tb01661a
  35. 35. Li Q, Jiang M, Wu G, Chen L, Chen S, Cao Y, et al. Photothermal conversion triggered precisely targeted healing of epoxy resin based on thermoreversible Diels-Alder network and amino-functionalized carbon nanotubes. ACS Applied Materials & Interfaces. 2017;9(24):20797-20807. DOI: 10.1021/acsami.7b01954
  36. 36. Li H, Chang C, Hsu K, Liu Y. Poly(lactide)-functionalized and Fe3O4 nanoparticle-decorated multiwalled carbon nanotubes for preparation of electrically-conductive and magnetic poly(lactide) films and electrospun nanofibers. Journal of Materials Chemistry. 2012;22(11):4855-4860. DOI: 10.1039/c2jm14689d
  37. 37. Wu C, Kao T, Li H, Liu Y. Preparation of polybenzoxazine-functionalized Fe3O4 nanoparticles through in situ Diels-Alder polymerization for high performance magnetic polybenzoxazine/Fe3O4 nanocomposites. Composites Science and Technology. 2012;72(13):1562-1567. DOI: 10.1016/j.compscitech.2012.06.018
  38. 38. Liu X, Zhu M, Chen S, Yuan M, Guo Y, Song Y, et al. Organic-inorganic nanohybrids via directly grafting gold nanoparticles onto conjugated copolymers through the Diels-Alder reaction. Langmuir. 2008;24(20):11967-11974. DOI: 10.1021/la8020639
  39. 39. Yang Y, Zhu B, Yin D, Wei J, Wang Z, Xiong R, et al. Flexible self-healing nanocomposites for recoverable motion sensor. Nano Energy. 2015;17:1-9. DOI: 10.1016/j.nanoen.2015.07.023
  40. 40. Garcia-Astrain C, Hernandez R, Guaresti O, Fruk L, Mijangos C, Eceiza A, et al. Click crosslinked chitosan/gold nanocomposite hydrogels. Macromolecular Materials and Engineering. 2016;301(11):1295-1300. DOI: 10.1002/mame.201600247
  41. 41. Shibata M, Teramoto N, Akiba T, Ogihara M. High-performance hybrid materials prepared by the thermo-reversible Diels-Alder polymerization of furfuryl ester-terminated butylene succinate oligomers and maleimide compounds. Polymer Journal. 2011;43(5):455-463. DOI: 10.1038/pj.2011.14
  42. 42. Rana S, Doehler D, Nia AS, Nasir M, Beiner M, Binder WH. "Click"-triggered self-healing graphene nanocomposites. Macromolecular Rapid Communications. 2016;37(21):1715-1722. DOI: 10.1002/marc.201700610
  43. 43. Li Y, Louarn G, Aubert P, Alain-Rizzo V, Galmiche L, Audebert P, et al. Polypyrrole-modified graphene sheet nanocomposites as new efficient materials for supercapacitors. Carbon. 2016;105:510-520. DOI: 10.1016/j.carbon.2016.04.067
  44. 44. Li J, Zhang G, Sun R, Wong C. A covalently cross-linked reduced functionalized graphene oxide/polyurethane composite based on Diels-Alder chemistry and its potential application in healable flexible electronics. Journal of Materials Chemistry C. 2017;5(1):220-228. DOI: 10.1039/c6tc04715g
  45. 45. Cai C, Zhang Y, Zou X, Zhang R, Wang X, Wu Q, et al. Rapid self-healing and recycling of multiple-responsive mechanically enhanced epoxy resin/graphene nanocomposites. RSC Advances. 2017;7(73):46336-46343. DOI: 10.1039/c7ra09258j
  46. 46. Zabihi O, Ahmadi M, Abdollahi T, Nikafshar S, Naebe M. Collision-induced activation: Towards industrially scalable approach to graphite nanoplatelets functionalization for superior polymer nanocomposites. Scientific Reports. 2017;7:3560. DOI: 10.1038/s41598-017-03890-8
  47. 47. Cai C, Zhang Y, Li M, Chen Y, Zhang R, Wang X, et al. Multiple-responsive shape memory polyacrylonitrile/graphene nanocomposites with rapid self-healing and recycling properties. RSC Advances. 2018;8(3):1225-1231. DOI: 10.1039/c7ra11484b
  48. 48. Kuang X, Liu G, Dong X, Wang D. Enhancement of mechanical and self-healing performance in multiwall carbon nanotube/rubber composites via Diels-Alder bonding. Macromolecular Materials and Engineering. 2016;301(5):535-541. DOI: 10.1002/mame.201500425
  49. 49. Hohlbein N, Shaaban A, Schmidt AM, et al. Polymer. 2015;69:301-309. DOI: 10.1016/j.polymer.2015.04.024
  50. 50. Engel T, Kickelbick G. Self-healing nanocomposites from silica - polymer core - shell nanoparticles. Polymer International. 2014;63(5):915-923. DOI: 10.1002/pi.4642
  51. 51. Doehler D, Michael P, Binder WH. CuAAC-based click chemistry in self-healing polymers. Accounts of Chemical Research. 2017;50(10):2610-2620. DOI: 10.1021/acs.accounts.7b00371
  52. 52. Heo Y, Malakooti MH, Sodano HA. Self-healing polymers and composites for extreme environments. Journal of Materials Chemistry A. 2016;4(44):17403-17411. DOI: 10.1039/c6ta06213j
  53. 53. Willocq B, Bose RK, Khelifa F, Garcia SJ, Dubois P, Raquez J. Healing by the joule effect of electrically conductive poly(ester-urethane)/carbon nanotube nanocomposites. Journal of Materials Chemistry A. 2016;4(11):4089-4097. DOI: 10.1039/c5ta09793b
  54. 54. Polgar LM, van Essen FCM, Hermosilla RA, Migliore N, Lenti M, Raffa P, et al. Thermoreversibly cross-linked EPM rubber Nanocomposites with carbon nanotubes Nanomaterials. Nanomaterials. 2018;8(2):58. DOI: 10.3390/nano8020058
  55. 55. Wu S, Li J, Zhang G, Yao Y, Li G, Sun R, et al. Ultrafast self-healing nanocomposites via infrared laser and their application in flexible electronics. ACS Applied Materials & Interfaces. 2017;9(3):3040-3049. DOI: 10.1021/acsami.6b15476
  56. 56. Schaefer S, Kickelbick G. Self-healing polymer nanocomposites based on Diels-Alder-reactions with silica nanoparticles: The role of the polymer matrix. Polymer. 2015;69:357-368. DOI: 10.1016/j.polymer.2015.03.017
  57. 57. Jo YY, Lee AS, Baek K, Lee H, Hwang SS. Thermally reversible self-healing polysilsesquioxane structure-property relationships based on Diels-Alder chemistry. Polymer. 2017;108:58-65. DOI: 10.1016/j.polymer.2016.11.040
  58. 58. Bai J, He Q, Shi Z, Tian M, Xu H, Ma X, et al. Self-assembled elastomer nanocomposites utilizing C-60 and poly(styrene-b-butadiene-b-styrene) via thermally reversible Diels-Alder reaction with self-healing and remolding abilities. Polymer. 2017;116:268-277. DOI: 10.1016/j.polymer.2017.03.080
  59. 59. Shahabadi SIS, Kong JH, Lu XH. Aqueous-only, green route to self-healable, UV-resistant, and electrically conductive polyurethane/graphene/lignin nanocomposite coatings. ACS Sustainable Chemistry & Engineering. 2017;5(4):3148-3157. DOI: 10.1021/acssuschemeng.6b02941
  60. 60. Imato K, Natterodt JC, Sapkota J, Goseki R, Weder C, Takahara A, et al. Dynamic covalent diarylbibenzofuranone-modified nanocellulose: Mechanochromic behaviour and application in self-healing polymer composites. Polymer Chemistry. 2017;8(13):2115-2122. DOI: 10.1039/c7py00074j

Written By

Ranjita K. Bose, Francesco Picchioni and Henky Muljana

Submitted: March 8th, 2018 Reviewed: July 10th, 2018 Published: November 5th, 2018