Self-healing materials are a class of smart materials that have the structurally incorporated ability to repair damage caused by mechanical usage over time. The inspiration comes from biological systems, which have the ability to heal after being wounded. Initiation of cracks and other types of damage on a microscopic level has been shown to change thermal, electrical, and acoustical properties, and eventually lead to whole scale failure of the material. Usually, cracks are mended by hand, which is difficult because cracks are often hard to detect. A material (polymers, ceramics, etc.) that can intrinsically correct damage caused by normal usage could lower production costs of a number of different industrial processes through longer part lifetime, reduction of inefficiency over time caused by degradation, as well as prevent costs incurred by material failure.[1] For a material to be defined as self-healing, it is necessary that the healing process occurs without human intervention. Some examples shown below include healing polymers that are not "self-healing" polymers.
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From a molecular perspective, traditional polymers yield to mechanical stress though cleavage of sigma bonds.[2] While newer polymers can yield in other ways, traditional polymers typically yield through homolytic or heterolytic bond cleavage. The factors that determine how a polymer will yield include: type of stress, chemical properties inherent to the polymer, level and type of solvation, and temperature.[2]
From a macromolecular perspective, stress induced damage at the molecular level leads to larger scale damage called microcracks.[3] A microcrack is formed where neighboring polymer chains have been damaged in close proximity, ultimately leading to the weakening of the fiber as a whole.[3]
Polymers have been observed to undergo homolytic bond cleavage through the use of radical reporters such as DPPH (2,2-Diphenyl-1-Picrylhydrazyl) and PMNB (Pentamethylnitrosobenzene.) When a bond is cleaved homolytically, two radical species are formed which can recombine to repair damage or can initiate other homolytic cleavages which can in turn lead to more damage.[2]
Polymers have also been observed to undergo heterolytic bond cleavage through isotope labeling experiments. When a bond is cleaved heterolytically, cationic and anionic species are formed which can in turn recombine to repair damage, can be quenched by solvent, or can react destructively with nearby polymers.[2]
Certain polymers yield to mechanical stress in an atypical, reversible manner.[4] Diels-Alder-based polymers undergo a reversible cycloaddition, where mechanical stress cleaves two sigma bonds in a retro Diels-Alder reaction. This stress results in additional pi-bonded electrons as opposed to radical or charged moieties.[1]
Supramolecular polymers are composed of monomers that interact non-covalently.[5] Common interactions include hydrogen bonds, metal coordination, and van der Waals forces.[5] Mechanical stress in supramolecular polymers causes the disruption of these specific non-covalent interactions, leading to monomer separation and polymer breakdown.
Reversible systems are polymeric systems that can revert to the initial state whether it is monomeric, oligomeric, or non-cross-linked. Since the polymer is stable under normal condition, the reversible process usually requires an external stimulus for it to occur. For a reversible healing polymer, if the material is damaged by means such as heating and reverted to its constituents, it can be repaired or "healed" to its polymer form by applying the original condition used to polymerize it.
Among the examples of reversible healing polymers, the Diels-Alder (DA) reaction and its Retro-Diels-Alder (RDA) analogue seems to be very promising due to its thermal reversibility. In general, the monomer containing the functional groups such as furan or maleimide form two carbon-carbon bonds in a specific manner and construct the polymer through DA reaction. This polymer, upon heating, breaks down to its original monomeric units via RDA reaction and then reforms the polymer upon cooling or through any other conditions that were initially used to make the polymer. During the last few decades, two types of reversible polymers have been studied: (i) polymers where the pendant groups, such as furan or maleimide groups, cross-link through successive DA coupling reactions; (ii) polymers where the multifunctional monomers link to each other through successive DA coupling reactions.[4]
In this type of polymer, the polymer forms through the cross linking of the pendant groups from the linear thermoplastics. For example, Saegusa et al. have shown the reversible cross-linking of modified poly(N-acetylethyleneimine)s containing either maleimide or furancarbonyl pendant moideties. The reaction is shown in Scheme 3. They mixed the two complementary polymers to make a highly cross-linked material through DA reaction of furan and maleimide units at room temperature, as the cross-linked polymer is more thermodynamically stable than the individual starting materials. However, upon heating the polymer to 80 °C for two hours in a polar solvent, two monomers were regenerated via RDA reaction, indicating the breaking of polymers.[6] This was possible because the heating energy provided enough energy to go over the energy barrier and results in the two monomers. Cooling the two starting monomers, or damaged polymer, to room temperature for 7 days healed and reformed the polymer.
The reversible DA/RDA reaction is not limited to furan-meleimides based polymers as it is shown by the work of Schiraldi et al. They have shown the reversible cross-linking of polymers bearing pendent anthracene group with maleimides. However, the reversible reaction occurred only partially upon heating to 250 °C due to the competing decomposition reaction.[7]
In this type of polymer, the DA reaction takes place in the backbone itself to construct the polymer, not as a link. For polymerization and healing processes of a DA-step-growth furan-maleimide based polymer (3M4F) were demonstrated by subjecting it to heating/cooling cycles. Tris-maleimide (3M) and tetra-furan (4F) formed a polymer through DA reaction and, when heated to 120 °C, de-polymerized through RDA reaction, resulting in the starting materials. Subsequent heating to 90–120 °C and cooling to room temperature healed the polymer, partially restoring its mechanical properties through intervention.[8] [9] The reaction is shown in Scheme 4.
The thiol-based polymers have disulfide bonds that can be reversibly cross-linked through oxidation and reduction. Under reducing condition, the disulfide (SS) bridges in the polymer breaks and results in monomers, however, under oxidizing condition, the thiols (SH) of each monomer forms the disulfide bond, cross-linking the starting materials to form the polymer. Chujo et al. have shown the thiol-based reversible cross-linked polymer using poly(N-acetylethyleneimine). (Scheme 5) [10]
Thus far, all of the examples on this page require an external stimulus to initiate polymer healing (such as heat or light). Energy is introduced into the system to allow repolymerization to take place. This is not possible for all materials. Thermosetting polymers, for example, are not remoldable. Once they are polymerized (cured), decomposition occurs before the melt temperature is reached. Thus, adding heat to initiate healing in the polymer is not possible. Additionally, thermosetting polymers cannot be recycled, so it is even more important to extend the lifetime of materials of this nature.
For the first method, fragile glass capillaries or fibers imbedded within a composite material. (Note: this is already a commonly utilized practice for strengthening materials. See Fiber-reinforced plastic.)[11] The resulting porous network is filled with monomer. When damage occurs in the material from regular use, the tubes also crack and the monomer is released into the cracks. Other tubes containing a hardening agent also crack and mix with the monomer, causing the crack to be healed.[12]
This method is similar in design to the hollow tube approach. Monomer is encapsulated and embedded within the thermosetting polymer. When the crack reaches the microcapsule, the capsule breaks and the monomer bleeds into the crack, where it can polymerize and mend the crack
In order for this process to happen at room temperature, and for the reactants to remain in a monomeric state within the capsule, a catalyst is also imbedded into the thermoset. The catalyst lowers the energy barrier of the reaction and allows the monomer to polymerize without the addition of heat. The capsules (often made of wax) around the monomer and the catalyst are important maintain separation until the crack facilitates the reaction.[4][13]
There are many challenges in designing this type of material. First, the reactivity of the catalyst must be maintained even after it is enclosed in wax. Additionally, the monomer must flow at a sufficient rate (have low enough viscosity) to cover the entire crack before it is polymerized, or full healing capacity will not be reached. Finally, the catalyst must quickly dissolve into monomer in order to react efficiently and prevent the crack from spreading further.[13] This process has been demonstrated with dicyclopentadiene (DCPD) and Grubbs' catalyst (benzylidene-bis(tricyclohexylphosphine)dichlororuthenium). Both DCPD and Grubbs' catalyst are imbedded in a epoxy resin. The monomer on its own is relatively unreactive and polymerization does not take place. When a microcrack reaches both the capsule containing DCPD and the catalyst, the monomer is released from the core-shell microcapsule and comes in contact with exposed catalyst, upon which the monomer undergoes ring opening metathesis polymerization (ROMP).[13] The metathesis reaction of the monomer involves the severance of the two double bonds in favor of new bonds. The presence of the catalyst allows for the energy barrier (energy of activation) to be lowered, and the polymerization reaction can proceed at room temperature.[14] The resulting polymer allows the epoxy composite material to regain 67% of its former strength.
Grubbs' catalyst is a good choice for this type of system because it is insensitive to air and water, thus robust enough to maintain reactivity within the material. Utilizing a live catalyst is important to promote multiple healing actions.[12] The major drawback is the cost. It was shown that using more of the catalyst corresponded directly to higher degree of healing. Ruthenium is a quite costly, which makes it impractical for commercial applications.
On August 3, 2010, University of Wisconsin-Milwaukee researchers demonstrated an aluminum-fly ash composite material, a self-healing metal which uses a similar "balloon" capsule deposition process during casting. This material has been formed into prototype engine components for field research by use in diesel truck engines (see UWM Researchers Work to Develop Self-Healing Metal).
Completely autonomous synthetic self-healing material was reported in 2001 on example of an epoxy system containing microcapsules.[15] These microcapsules were filled with a (liquid) monomer. If a microcrack occurs in this system, the microcapsule will rupture and the monomer will fill the crack. Subsequently it will polymerise, initiated by catalyst particles (Grubbs catalyst) that are also dispersed through the system. This model system of a self healing particle proved to work very well in pure polymers and polymer coatings.
A hollow glass fibre approach may be more appropriate for self-healing impact damage in fibre-reinforced polymer composite materials. Impact damage can cause a significant reduction in compressive strength with little damage obvious to the naked eye. Hollow glass fibres containing liquid healing agents (some fibres carrying a liquid epoxy monomer and some the corresponding liquid hardener) are embedded within a composite laminate. Studies have shown significant potential.[16]
In addition to the sequestered healing agent strategies described above, research into "intrinsically" self-healing materials is also being performed. For example, supramolecular polymers are materials formed by reversibly connected non-covalent bonds (i.e. hydrogen bond), which will disassociate at elevated temperatures. Healing of these supramolecullary based materials is accomplished by heating them and allowing the non-covalent bonds to break. Upon cooling new bonds will be formed and the material will potentially heal any damage. An advantage of this method is that no reactive chemicals or (toxic) catalysts are needed. However, these materials are not "autonomic" as they require the intervention of an outside agent to initiate a healing response.
Self-healing materials are widely encountered in natural systems, and inspiration can be drawn from these systems for design. There is evidence in the academic literature[17] of these biomimetic design approaches being used in the development of self-healing systems for polymer composites.[18]
At least one company is attempting to bring these new materials to the market, Autonomic Materials Inc.,with a product expected in 2009.[19]