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Self-healing material
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 unsatisfactory 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. For a material to be defined strictly as self-healing, it is necessary that the healing process occurs without human intervention. Some examples shown below, however, include healing polymers that require intervention to initiate the healing process.
Polymer breakdown
From a molecular perspective, traditional polymers yield to mechanical stress though cleavage of sigma bonds. 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. From a macromolecular perspective, stress induced damage at the molecular level leads to larger scale damage called microcracks. 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.
Self-healing material
Supramolecular breakdown
Supramolecular polymers are composed of monomers that interact non-covalently. Common interactions include hydrogen bonds, metal coordination, and van der Waals forces. Mechanical stress in supramolecular polymers causes the disruption of these specific non-covalent interactions, leading to monomer separation and polymer breakdown.
Self-healing material
Scheme 3. Reversible polymer cross-linking via Diels-Alder cycloaddition reaction between furan and maleimide.
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. Polymerization of multifunctional monomers 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 90120 C and cooling to room temperature healed the polymer, partially restoring its mechanical properties through intervention. The reaction is shown in Scheme 4.
Self-healing material
Thiol-based polymers 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)
Self-healing material Poly(urea-urethane) A soft poly(urea-urethane) network leverages the metathesis reaction in aromatic disulphides to provide room-temperature self-healing properties, without the need for external catalysts. This chemical reaction is naturally able to create covalent bonds at room temperature, allowing the polymer to autonomously heal without an external source of energy. Left to rest at room temperature, the material mended itself with 80 percent efficiency after only two hours and 97 percent after 24 hours.
Self-healing material Discrete channels Discrete channels can be built independently of building the material and are placed in an array throughout the material. When creating these microchannels, one major factor to take into account is that the closer the tubes are together, the lower the strength will be, but the more efficient the recovery will be. A sandwich structure is a type of discrete channels that consists of tubes in the center of the material, and heals outwards from the middle. The stiffness of sandwich structures is high, making it an attractive option for pressurized chambers. For the most part in sandwich structures, the strength of the material is maintained as compared to vascular networks. Also, material shows almost full recovery from damage. Interconnected networks Interconnected networks are more efficient than discrete channels, but are harder and more expensive to create. The most basic way to create these channels is to apply basic machining principles to create micro scale channel grooves. These techniques yield channels from 600700 micrometers. This technique works great on the two-dimensional plane, but when trying to create a three-dimensional network, they are limited. Direct Ink Writing The Direct Ink Writing (DIW) technique is a controlled extrusion of viscoelastic inks to create three-dimensional interconnected networks. It works by first setting organic ink in a defined pattern. Then the structure is infiltrated with a material like an epoxy. This epoxy is then solidified, and the ink can be sucked out with a modest vacuum, creating the hollow tubes.
Microcapsule healing
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
Figure 1. Depiction of crack propagation through microcapsule-imbedded material. Monomer microcapsules are represented by pink circles and catalyst is shown by purple dots.
A good way to enable multiple healing events is to use living (or unterminated chain-ends) polymerization catalysts. If the walls of the capsule are created too thick, they may not fracture when the crack approaches, but if they are too thin, they may rupture prematurely. 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. 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
Self-healing material further. This process has been demonstrated with dicyclopentadiene (DCPD) and Grubbs' catalyst (benzylidene-bis(tricyclohexylphosphine)dichlororuthenium). Both DCPD and Grubbs' catalyst are imbedded in an epoxy resin. The monomer Scheme 6. ROMP of DCPD via Grubbs' catalyst 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 coreshell microcapsule and comes in contact with exposed catalyst, upon which the monomer undergoes ring opening metathesis polymerization (ROMP). 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. 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. Using a live catalyst is important to promote multiple healing actions. The major drawback is the cost. It was shown that using more of the catalyst corresponded directly to higher degree of healing. Ruthenium is quite costly, which makes it impractical for commercial applications.
SLIPS
A different approach was suggested by Prof. J. Aizenberg from Harvard University, who suggested to use Slippery Liquid-Infused Porous Surfaces (SLIPS), a porous material inspired by the carnivorous pitcher plant and filled with a lubricating liquid immiscible with both water and oil. SLIPS possess self-healing and self-lubricating properties as well as icephobicity and were successfully used for many purposes.
Self-healing material monomer and some the corresponding liquid hardener) are embedded within a composite laminate. Studies have shown significant potential.
Biomimetics
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 of these biomimetic design approaches being used in the development of self-healing systems for polymer composites. In biology, for the minimum power to pump fluid through vessels Murray's law applies. Deviation from Murrays law is small however, increasing the diameter 10% only leads to an additional power requirement of 3%5%. Murrays law is followed in some mechanical vessels, and using Murrays law can reduce the hydraulic resistance throughout the vessels. The DIW structure from above can be used to essentially mimic the structure of skin. Toohey et al. did this with an epoxy substrate containing a grid of microchannels containing dicyclopentadiene (DCPD), and incorporated Grubbs' catalyst to the surface. This showed partial recovery of toughness after fracture, and could be repeated several times because of the ability to replenish the channels after use. The process is not repeatable forever, because the polymer in the crack plane from previous healings would build up over time.
Further applications
Self-healing epoxies can be incorporated on to metals in order to prevent corrosion. A substrate metal showed major degradation and rust formation after 72 hours of exposure. But after being coated with the self-healing epoxy, there was no visible damage under SEM after 72 hours of same exposure.
History
Self healing materials only emerged as a widely recognized field of study in the 21st century. The first international conference on self-healing materials was held in 2007. The field of self-healing materials is related to biomimetic materials (materials inspired by living nature) as well as to other novel materials and surfaces with the embedded capacity for self-organization, such as the self-lubricating and self-cleaning materials. However, some of the simpler applications have been known for centuries, such as the self repair of cracks in concrete. Related processes in concrete have been studied microscopically since the 19th century. A form of self healing mortar was known even to the ancient Romans.
Self-healing material
Commercialization
At least one company is attempting to bring the newer applications of self healing material to the market. As of 2012, Autonomic Materials Inc., had raised over three million US dollars.[1]
References
[1] Bourzac, Katherine First Self-Healing Coatings (http:/ / www. technologyreview. com/ business/ 21812/ ?a=f). technologyreview.com. December 12, 2008.
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License
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