THE 'BIO-INSPIRED' MATERIALS THAT SELF-REPAIR

A.Keerthana, P.Maheswari akeerthana1995@gmail.com mahes3777@gmail.com Abstract: Self-healing materials possess tremendous potential in increasing the longevity of structural materials. Consequently, a large number of academic and industrial research organizations have come forward to explore new concepts in design and synthesis of such materials. Though this field of innovative product research shows high promises, it has some practical limitations in understanding crack healing kinetics and stability of healing functionality. In this paper, different types of healing processes, design strategies and specific applications are reviewed.

Keywords: self-healing materials, autonomic process, non-autonomic process, design, applications

Introduction Self-healing materials are no more an illusion and we are not far away from the days when manmade materials can restore their structural integrity in case of a failure. For example, the cracks in buildings can close on their own or the scratches on car bodies can recover their original shiny appearance by itself. Indeed, this is what everyone can see in case of the natural healing of wounds and cuts in living species. Virtually, all materials are susceptible to natural or artificial degradation and deteriorate with time. In the case of structural materials the long-time degradation process leads to micro cracks that causes a failure. Thus, repairing is indispensable to enhance reliability and lifetime of materials. Though scientists are inspired by the natural process of blood clotting or repairing of fractured bones, incorporating the same concept into engineering materials is far from reality due to the complex nature of the healing processes in human bodies or other animals. However, the recent announcement from Nissan on the commercial release of scratch healing paints for use on car bodies has gained public interest on such a wonderful property of materials. Self-healing materials are those that have a potential to repair mechanical damages and cracks caused by over-usage, without the need for human interference. The key potential benefits of selfhealing materials are as follows:

Minimizing the production cost of various industrial processes required for repairing damage. Prolonging the service life of the materials.

Reducing the inefficiency of the materials due to degradation. Definition of Self-healing Self-healing can be defined as the ability of a material to heal (recover/repair) damages automatically and autonomously, that is, without any external intervention. Many common terms such as self-repairing, autonomic-healing, and autonomic-repairing are used to define such a property in materials. Incorporationof self-healing properties in manmade materials very often cannot perform the self-healing action without an external trigger. Thus, self-healing can be of the following two types: autonomic (without any intervention); non autonomic (needs human intervention/external triggering). Here, in this review, different types of healing processes are considered as self-healing in general. Currently, self-healing is only considered as the recovery of mechanical strength through crack healing. However, there are other examples where not only the cracks but also small pin holes can be filled and healed to have better performance. Thus, this review addresses recovery of different types of properties, of materials. How Self-healing Materials Work Although self-healing materials facilitate good mechanical performance, they are restricted to autonomic healing of damage in a particular location. These polymers function based on a three-step process, which is similar to that of a biological response. The first step involves triggering action immediately after the damage occurs. The second step is the transportation of materials to an affected region. The third step involves the chemical repair process. Self-healing materials are divided into 3 general sub-categories: capsule-based materials, vascular materials and intrinsic materials. In the capsule-based materials, the healing agent is contained within the small capsules that release the agent upon rupture. The healing agent is present inside the capillary type hollow channels in case of vascular materials, and the channels are capable of being interconnected onedimensionally, two-dimensionally or three-dimensionally. The capillary network can be refilled by an external source or another channel that remains undamaged. Intrinsic self-healing materials function on latent self-healing property rather than using healing agent. However, with the recent advancements of various new lithographic techniques, self-healing materials with complex embedded micro vascular networks for autonomously repairing repeated damage events are being developed. This micro vascular coatingsubstrate architecture of the materials is similar to that of a human skin. The self-healing material structure is composed of a

micro vascular substrate containing micro vascular network filled with a healing agent and a brittle epoxy coating containing catalyst particles. When a coating-substrate beam is loaded in a four-point bending configuration, the cracks are developed at a coating surface and propagated towards a coatingsubstrate interface. The healing agent is released into the cracks when the coating is damaged, through capillary action. Excess healing agent is secreted on the surface of the coating. The cracks are repaired after a sufficient time period, which leads to the restoration of structural integrity of the coating. The healing cycle is repeated when the cracks reopen. Applications Product commercialization in industries is usually based on the following major milestones: idea generation (preliminary level) laboratory implementation (product level) pilot line up scaling (process level) industrial applications (marketing level). Currently, self-healing materials development is either in the preliminary or product level, and so these materials are yet to be available for many applications. Applications of self-healing materials are expected almost entirely in all industries in future. The very few applications being developed to date are mainly in the automotive, aerospace, and building industries. For example, Nissan Motor Co. Ltd has commercialized worlds first self-healing clear coat for car surfaces. The trade name of this product is Scratch Guard Coat. According to the company, this hydrophobic paint repairs scratches (arising from car washings, off-road driving, or fingernails) on coated car surfaces and is effective for a period of three years. This newly developed paint contains high elastic resins that prevent scratches reaching the inner layers of a painted car surface. Depending on the depth of the scratch and the temperature in the surrounding environment, the entire recovery occurs between 1 and 7 days. Another example in this category is the two component polyurethane clear coats from Bayer Material Science. The trade names of the raw materials used to formulate this coating are Desmodur and Desmophen. According to company sources this coating heals small scratches under the influence of heat (sunlight) and the trick employed to design such coatings is based on the use of dense polymer networks with flexible linkages. For both the above examples the scratch discussed is in the range of few micrometers, which is obviously visible to the naked eye, and therefore the products are suitable for keeping the aesthetics of the coating. Moreover, the above examples also follow similar self-healing mechanisms. Energy required to overcome the resistance of materials to create a scratch is higher in the case of thermosetting polymers (proportional to its plastic and/or elastic response) compared to thermoplastic polymers (viscoelastic response). Formation of a scratch in materials leads transport of materials from the affected zone to its side leaving the groove. In case

of thermoplastic polymers, the energy is lost in the process of viscous flow in the absence of residual stress (due to viscoelastic or plastic deformation).Thus the most important driving force that helps the reflow of materials from the side to the groove is surface tension. However, for thermosetting polymers, the energy (below it yields strength) incorporated to create a scratch is stored in the neighborhood of the conduit. When the mechanical stress is removed, the stored energy is relieved and the distorted polymer chains returns leveling the groove. This recovery process is highly dependent on the mobility of the polymer chains that is on their glass transition temperature.

Scratching

Heating

Fig.Schematic showing the reflow effect of self-healing clear coats [adapted from a presentation [100] of Bayer Materials Science].

However, while scratching, if the mechanical stress also leads to cracking besides scratch formation, the stored energy will be released at the inappropriate time and a partial recovery (plastic residual strain allows some reflow) may be expected as surface tension-driven viscous process will not take place here due to the presence of opposing elastic force in the system. Thus, scratch with fractures is a permanent damage for thermosetting polymers, and therefore a compromise has to be considered between the above two processes for designing self-healing polymer coatings. External trigger can be useful in this case. Thus, polymers with high Tg (less material transport) incombination with high elastic response could be an option for the recovery of small scratches. In case of small fractures, triggering by temperature will enhance the mobility of the polymer chains and surface tension will play an important role for self-healing. The next industrial segment where applications of self-healing materials are foreseen is the aviation industry. Use of composites in aircrafts has grown significantly in the past years. Hollow fibers reinforced composites are a

possible solution to recover cracking or damages. Self-healing polymers have paved its way in space applications. The construction industry will also find many applications of self-healing materials. For example, self-healing concretes may become a reality soon. Self-healing corrosion resistant coatings could be beneficial for structural metallic components such as steel for achieving long-term service life with reduced maintenance cost. Other areas of applications of self-healing materials are in medical segments. Biocompatible self-healing composite may extend the service life of artificial bone, artificial teeth, and so on. The very recent discovery of self-healing rubber may find applications in the toy industry. Finally, it could be said that the available technologies to design self-healing materials are not cost effective. This limits the wide use of these materials for different commercial applications. In future, one can expect to see new technologies that will enable the possibility of using self-healing materials in our day-to-day life. Self-healing systems can be developed from a variety of metallic materials and polymers. Carbon nano tubes (CNTs) are now considered as an ideal material for mechanical reinforcement purpose and molecular storage devices as well. This is mainly due to the fact that CNTs have a large interfacial area, good mechanical and chemical properties and a hollow tubular structure despite their small structure. Polymer/CNTs composites have provided favorable results for self-healing applications in storage devices. Currently, innovative self-healing nano systems are being developed with the help of computer simulations for repairing damages. Potential future uses for self-healing plastics include longer lasting cell-phones, cars and laptops, whilst larger scale structures will also benefit, from aeroplanes to spacecraft. The future possibilities for these smart materials look to be almost limitless. Conclusion Micro cracking and hidden damages are the initiators for structural failures. On the other hand, high maintenance and repairing costs limit the acceptance of different materials in engineering disciplines. Repairing at remote locations is very difficult. In this context, self-healing materials possess tremendous potential in increasing the longevity of structural materials. Consequently, a large number of academic and industrial research organizations have come forward to explore new concepts in this promising filed. A growing trend of investments is also being seen from both the government and industrial funding agencies. Though this field of innovative product research shows high promises, it has some practical limitations in understanding crack healing kinetics and stability of healing functionality. Thus the main challenge of self-healing material development is autonomic detection of cracks and its subsequent healing. To be able to develop new innovative solutions based

on biomimetic approaches, it is an ultimate need to overcome the difficulties of damage detection and achievingan autonomic-healing phenomenon. Besides autonomic-healing, nonautonomic processes will also find industrial applications. It is sure that this wonderful field of self-healing materials will continue to grow beyond the technologies reviewed. References: [1] Weiner, S. and Wagner, H.D. 1998 Annual Review of Materials Science, 28, 27198. [2] Zhou, B.L. 1996. Materials Chemistry and Physics, 45 (2), 11419. [3] Fratzl, P. and Weinkamer, R. 2007. In Self Healing Materials. An Alternative Approach to 20 Centuries of Materials Science (ed S. vanderZwaag) , Springer,pp. 32335. [4] Vermolen, F.J., van Rossum,W.G., Javierre, E. and Adam, J.A. 2007. Self Healing Materials. An Alternative Approach to 20 Centuries of Materials Science (edS.vanderZwaag), Springer, pp. 337 63. [5] Kessler, M.R. 2007. Proceedings of the Institution of Mechanical Engineers Part G-Journal of Aerospace Engineering, 221, 47995. [6] Wool, R.P. 2008. Soft Matter, 4,40018. [7] http://www.nissan-global.com/EN/TECHNOLOGY/INTRODUCTION/DETAILS/SGC/index.html. (Access year 2008). [8] Trask, R.S. and Bond, I.P. 2006.Smart Materials and Structures, 15,70410. [9] Motuku, M., Vaidya, U.K. and Janowski, G.M. 1999. Smart Materials and Structures, 8, 62338. [10] Bergman, S.D. and Wudl, F. 2007. van der Zwaag, S. (ed.)Self-healing materials. An Alternative Approach to 20 Centuries of materials Science, Springer, pp. 4568.

THE BIO-INSPIRED MATERIALS THAT SELF-REPAIR

PRESENTE BY A.KEERTHANA (13CSR080) P.MAHESWARI (13CSR093)

CSE-B