Vol.2, No.8, 873-901 (2010) Natural Science http://dx.doi.org/10.4236/ns.2010.28110 Copyright © 2010 SciRes. OPEN ACCESS Self-repairing material systems―a dream or a reality? Hartmut Fischer1,2 1TNO Science and Industry, Eindhoven, The Netherlands; 2CSIRO Material Science and Engineering, Clayton South, Australia; hartmut.fischer@tno.nl Received 21 April 2010; revised 22 June 2010; accepted 27 June 2010. ABSTRACT Currently, most industrial materials rely entirely on passive protection mechanisms; such me- chanisms are readily applicable and universal for many different materials systems. However, they will always stay passive, and therefore their lifetime and functionality is limited and related to the amount of protective additives and the intensity of their consumption. Therefore, better, and preferentially active process for the protec- tion/repair of damaged materials―self-repairing- processes―were developed and need to be developed further. Although it sounds futuristic or like a fiction in the modern, trendy times, which in many ways affects also directions of research; self healing of material systems exists already for a long time in all sorts of systems of materials or functionalities. The aim of this work is to go beyond the scope of a classical review the ones published recently in this field which almost entirely focused only onto polymeric systems. In this work, an analysis of the under- lying functional and constructional principles of existing natural and synthetically self-healing systems spanning over a range of classes of materials is given leading to general rules and principles for the design of new and application tailored self-healing material systems. Keywords: Self Healing; Systems; Sensors 1. INTRODUCTION Self-healing is an intrinsic property of living organisms, enabling them to cope with all sorts of damage or injury they experience during their lifetime. This repair occurs with essentially no external intervention. Thus, wounds heal, broken bones heal, and even lost parts of living bodies (lizard tails etc.) can be replaced in some cases. Some natural self-healing composite systems such as bones go beyond simple healing to the extent that they remodel themselves continuously. Damaged material is removed and replaced by new material and over-de- signed material is also removed and structures under stress are enhanced by additional material. To enable this process, specific cells entrapped in the bone tissues act as strain sensors and feel large deformations. Subse- quently, signals are sent to cells responsible for remov- ing or forming material (bone) [1]. In order to deal with the phenomenon and the con- nected principles of self-healing in general, and even further to design and construct artificial self-healing functionalities for systems and devices, it is important to understand the nature and the consequences of damage and of degradation processes first. Damage in general terms can be described as changes introduced to a system that affect its function and/or performance. That means that damage is not meaningful without a comparison of two different states of the sys- tem in question, one of which is assumed to be the initial (and often un-damaged) state. The term damage does not necessarily imply a total loss of system functionality, but rather a departure in level of system operation from op- timal. A fundamental challenge is the fact, that damage is typically a local phenomenon and may be therefore difficult to detect (in time) [2]. Most materials (systems) lose their integrity, their value, operation or usefulness over time due to degrada- tion processes where defects grow and coalesce to cause component and finally system level damage (e.g. fatigue or corrosion damage accumulation). On a relatively short time scale, damage can also result from scheduled dis- crete events such as aircraft landing and from unsched- uled discrete events such as an impact. As damage grows, it will reach a point where it affects the system operation to a level, which is not any longer acceptable for a user; this point is referred to failure. The main causes of deterioration of materials may be summarised as: 1) Harmful materials, substances and agents such as oxygen, oxidizing agents, water, salts, poisons, active materials, and living bodies such as virus, bacteria, fungi,
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 874 insects, animals, human beings and others, 2) Factors from the surroundings such as heat, visible light, external mechanical force e.g. strong wind, radia- tion, pressure, rain, collapse of the adjacent structure, a sudden impact and others. Such deterioration (or damage) are in general irre- versible, they occur progressively and exponentially in time until a certain threshold is reached where either significantly high costs for repairs are necessary or a (fatal) failure is going to occur. Increased lifetime and reliability of materials systems and devices can be criti- cal requirements in traffic, construction, information transfer, medicine, military, space missions as well as in ordinary daily life. In order to prevent such detoriation the following response mechanisms are known: PASSIVE (Built-in damage prevention): by protec- tion agents, that are directly attacked by the deterioration and the concentration of the agent is directly related to the amount of protection and that provide no repairabil- ity and hence no memory of the inherent structure. ACTIVE (Autonomous or self-repair): here the dete- rioration attacks directly atoms and molecules of the material itself instead of protection agents. The amount of repairing agents needed depends on the concentration of damaged sites and the accumulation of damage in time and at certain locations as well as on the repair rate; a transfer of material is needed and a memory of the original structure is preferable. The pictures in Figure 1 show schematically the de- scribed mechanisms applied to the case of polymers ma- trices as damaged material. Currently, most industrial materials rely entirely on passive protection mechanisms; such mechanisms are readily applicable and universal for many different ma- terials systems. However, they will always stay passive, and therefore their lifetime and functionality is limited and related to the amount of protective additives and the intensity of their consumption. Therefore, better, and preferentially active processes for the protection/repair of damaged materials―self- repairing-processes―were developed and need to be developed further. Although it sounds futuristic or like a fiction in the modern, trendy times, which in many ways affects also directions of research; self healing of mate- rial systems exists already for a long time in all sorts of systems of materials or functionalities. The aim of this work is to go beyond the scope of a classical review which almost entirely focused only onto polymeric systems like the ones published recently in this field [4-6]. In this work, an analysis of the underly- ing functional and constructional principles of existing natural and synthetically self-healing systems spanning over a range of classes of materials is given leading to general rules and principles for the design of new and application tailored self-healing material systems. Therefore, specific choices from the existing literature Figure 1. Passively protective mechanism versus active protective mechanism. Reference [3]: 1) Degradation factors are prevented from interacting with polymer chains, 2) Concentration of stabilizer deteriorates, 3) Degradation factors in- teract directly with polymer chains, 4) Degradation of polymeric chains, 5) Degradation factors directly interact with polymer chains and degradation occurs temporarily, 6) Cleavage of main chain, 7) Catalytic re-bonding reaction occurs, 8) Catalyst becomes reactivated.
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 875 have been made for this analysis, which either show new principles or contribute to this aim without repeating already existing systems in a similar or slightly different way. In the next section, a discussion of the phenomenon of repair and especially self-repair is presented, together with the principal design features and requirements that enable a self-repair to take place. Examples of self-repairing systems in material and life science starting with assisted (stimulated) repairing and of self repairing systems already known or currently under development are discussed in Section 3. This is followed by a discussion of the sensors and triggers em- ployed or potentially employable in self-healing systems in Sections 4 and 5. Finally, conclusions are drawn with respect to requirements for the design of self-healing systems and working areas necessary to concentrate on are presented (in the Sections 6 and 7). 2. WHAT IS SELF REPAIR? Repair itself is a process which can be initiated after damage on a local or global scale of a given functional system with the aim, to reduce the local or global level of damage and to extend or to renew the functionality and life-time of the damaged part, system or device. Self-repair is then in principle an autonomically initi- ated response to damage or failure. In order to perform this repair, any self-repair system must be capable of 1) identifying and 2) repairing failures. If failure is classi- fied as ‘any occurrence, which results in the system de- viating from its original task or not being any more able to fulfil its function’, what is than ultimately classified as ‘repair’? (Self) repair can be classified under two sig- nificant approaches: Attributive repair and Functional repair Attributive repair are attempts to restore the attrib- utes of the system to their original state, the full capacity of the system. Functional repair are attempts to restore the function of the system. If full functionality cannot be restored, this strategy attempts to focus the remaining available resources to maximise the available functionality. Attributive repair is the optimal solution. If the at- tempt to restore the system to its complete original con- dition fails, there is still significant benefit to be gained in most instances if the system continues to operate, even with reduced functionality. Attributive self-repair is an intrinsic property of nature. Figure 2 shows a schematic example of the steps in a self-repair cycle in nature, in this case bone failure due to fracture. This autonomic healing is initiated by the (a) (b) (c) (d) (e) Figure 2. Schematic picture of the healing stages of bone: a) internal bleeding (sensor), forming of a fibroin cloth; b) unor- ganized fiber mesh develops (first step of (primitive) repair); c) calcinations of the fibrocartilage (second step of repair); d) calcification converted into fibrous bone (structural repair); e) transformation into lamellar bone (complete recovery of intrin- sic structure and functionality) [7]. local damage of the vascular blood system. Healing a bone requires energy in the form of nutrition together with the delivery of cell material to the fracture site by the network of blood vessels; for healing a sufficient healing time must elapse. The healing process consists of multiple stages of deposition and assembly of material. Mimicking nature is the ultimate goal for materials designers and developers. There are essentially two design approaches to realize self-repairing systems: 1) a conventional design modifying existent design philosophies by incorporating intelligent techniques at the design stage to obtain a system with sufficient autonomous capabilities to initiate and effect a func- tional and in ideal cases an attributive repair. 2) a radically new design philosophy, where the sys- tem is designed in a cellular structure such that each cell contains a (genetic) code, which defines and determines its functionality. This term is called embryonics and it attempts to replicate the cellular structure of organisms in nature and their inherent self-replicating and thus self-healing capabilities resulting mostly in attributive repair. Although both strategies will certainly lead to new self-repairing systems, the conventional process will be easier to implement in the short term. Generally, self-repair processes in smart systems should not only replace any passive protection mecha- nism but should finally lead to structures, which are able to sense its internal state, to monitor the healthiness of the material/functionality/system/device at any time and at any location and respond in a manner that fulfils its functional requirements based on the gained informa- tion―sensing/detection, diagnosis of failure and activat- ing of repair! In order to perform properly, a smart system must have incorporated (embedded or surface mounted) ac-
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 876 tuation and sensor elements which offer the capacity of health monitoring (to be able to diagnose, interpret and correct structural faults in situ as they occur) by meas- urement of physical quantities such as vibration, perme- ability, current flow, strain, acoustic emission, imped- ance, pH-changes, colour tracers, etc., that are informa- tive with respect to the state of structural health. Meth- ods and instruments are X-ray tomography, ultrasonic methods and eddy current methods and strain- gauges, optical fibres, piezos and in general “smart tagged” composites. Specifically, information relating to the severity, sig- nificance and location of damage is required. Therefore, a detection of: 1) Damage occurrence, 2) Damage location, 3) Damage type 4) Damage force magnitude and consequently 5) The remaining lifetime of the structure is necessary for maintaining the functionality of the material/struc- ture/device. The information obtained has to be fed into the recovery cycle as sketched in Figure 3. The interpretation and operational evaluation of the obtained data may include on top of the data acquisition a normalisation and filtering process, a feature selection and information condensation and finally a statistical model development for feature discrimination. This di- agnosis will lead to an eventual initiation of the repair action. Finally, to perform a repair action, mobile parts are needed to be transported to the location of the damage. This can be realised using a liquid either locally avail- able or available via a vascular network system like the blood system in living organisms but also a transport via the gas phase is possible, in case material for the repair action is needed. Self-healing or self-repair can therefore in summary be defined as “the ability to substantially return to an initial, proper operating state or condition prior exposure to a dynamic environment by making the necessary ad- justments to restore to normality and/or the ability to resist the formation of irregularities and/or defects”. It is a much more effective damage management decreasing damage level during certain stages of life time than pas- sive prevention, since it is only applied in cases, times and locations of real need―damage which jeopardizes the functionality of a given system. Ideally, a self-heal- ing system will therefore display an unlimited lifetime since the rate of damage formation is negative or zero. Figure 3. Health monitoring and repair cycle for an active smart self-repairing system [8]. The system monitor must be able to analyse system performance against predefined per- formance benchmarks in order to continuously verify correct operation of the process. The testing process also must have bi-directional communication to activate specific test se- quences and receive results. This process should exploit any built -in self-test ability, and the testing results are forwarded to the diagnostic process. Automating the fault diagnosis process inherently demands the application of intelligent techniques. Finally, the self-repair process must be able to affect a repair based on the reduction in resources available, following isola- tion of the faulty components. If the original level of perform- ance cannot be restored, the monitoring system must be modi- fied to reflect the changes in system characteristics. This fea- ture demands an optimisation capability. Reprinted from Engi- neering Applications of Artificial Intelligence, Self-repair of embedded systems, 17, E. A. Coyle, L. P. Maguire, T. M. McGinnity, 1-9, Copyright (2004), with permission from El- sevier. 3. EXAMPLES OF SELF REPAIRING SYSTEMS IN MATERIAL AND LIFE SCIENCE In this section a number of existing self-repair systems is critically analysed with respect to its design, functional units/modules and their action/performance. Within all classes of materials, the self-repair potential of polymers is probably the largest of all materials, since the polymeric nature offers more possibilities of devel- oping and displaying molecular mobility than any other material. However, and as discussed below, this does not exclude other materials from a participation in functional self-healing systems. The different options for the design of the repair ac- tion of a polymeric based system connected with exam- ples of how this can be realized are illustrated in Figure
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 877 4 [9] and will be discussed in the following paragraphs. Essentially a differentiation between nature-analogous true autonomous self-repairing systems and other sys- tems, which may be only able to react onto damage and to make the necessary adjustments to restore itself to normality with human intervention, and may be there- fore better called assisted healing systems, can be made. Assisted (local) healing can be achieved, e.g. by an in- crease of temperature, by irradiation or by other stimuli. 3.1. Thermally Stimulated Repair A repair of accumulated damage may be triggered by thermal stimulation where the system allows the flow of material, wetting of the crack surfaces and gluing them together in a heating-cooling cycle. This can be most easily achieved in a system contain- ing polymeric chains, which during the transition from the glassy to the rubbery state experience a huge in- crease in mobility and hence the possibility to re-entan- gle after physical separation. The model to explain the movement of a polymer molecule in a snake-like fashion inside a cross-linked polymeric gel, also known as the reptation model as proposed by de Gennes [10] implies also a possibility of polymeric chains to repair damage. Prager and Tirell [11], Jud and Kausch [12] and later Wool and O’Connor [13] used the same reptation model to determine the time required for healing caused by the inter-diffusion of molecules between crack faces and thus re-gaining strength by annealing just above the Tg. Kim and Wool [14] predicted theoretically the recovery process as a function of healing time confirming existing experimen- taldata [15]. Also, it has been shown that, if amorphous bulk samples of high-molecular-weight polystyrene (PS) were brought into contact with themselves in a lap-shear joint geometry below the bulk glass transition tempera- ture, an increase in lap-shear strength and fracture oc- curred [16,17]. This can be attributed to the time–tem- perature shift of the glass transition, as well as to the possible enhanced surface molecular mobility of poly- mer chains leading to a lower Tg at free polymer surfaces compared to the bulk Tg which enables inter-diffusion of chains and self-healing even below Tg! At the present time, a decrease in density and a decrease in the entan- glement density close to the polymer surface can be con- sidered as the factors contributing to the increased mo- lecular mobility at polymeric surfaces in comparison with that in the bulk [18]. In addition to these factors, a "jump" in the conformational entropy of the chain segments lo- cated at the surface (these segments have a decreased entropy imposed by the polymer-air interface [19] upon the contact of the surfaces) may be considered as one of the driving forces of inter-diffusion across the interface. In principle, self-repairing polymers can therefore be realized essentially attributed to molecular inter-diffu- sion. Polymer networks with dangling chains can there- Figure 4. Organization of self-healing polymer based material systems according to the different principles employed adapted from [9].
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 878 fore be employed to heal cleavages at room temperature without any manual intervention [20]. However, self-repair needs time and rest. In a later study, the concept of re-entanglement of polymeric chains by reptation has been applied in thermoset composite materials where a linear thermoplastic polymer material was inserted into an epoxy matrix leading to a recovery of up 70% of the fracture toughness [21]. In this case as in the previous cases, multiple repairs are possible [22]. Alternatively, Zako and Tanako embedded small grain- particle adhesives in a glass epoxy composite laminate [23] an Meure, Wu and Furman polyethylene-co-me- thacrylic acid particles in an epoxy resin [24] to act as repair agents. The 50 micron sized particles consisted of thermosetting type epoxy; the matrix was a cold-setting epoxy. Damage can be repaired by the particles acting as repairing actuator when melted by heat. A similar mecha- nism can be used for the thermally stimulated self-repair of glass-ceramic composites, here heals the flow of the viscoelastic glass matrix at higher temperatures aging induced micro-voids in the composite material [25]. A very efficient and fast assisted repairing system by external stimulation consist just of one material capable of fulfilling all functions (structural properties, sensor and providing of mobility) by reversible formation of covalent or non-covalent bonds (ionic or H-bonds). Thermally controlled covalent bond formation is already long known in organic chemistry and may be applied to the formation of linear polymers as well as to the forma- tion of polymer networks. Besides thermally reversible urea [26], alkoxyamine units incorporated in the main chain [27], nitroso-dimerisation and ester formation un- der presence of cyclic anhydrides [28], the (4 + 2) Di- els-Alder reaction is by far the most important reaction. It was already discovered in 1928 [29] and honoured with the Nobel Prize in 1950 and generally considered the "Mona Lisa" of reactions in organic chemistry since it requires very little energy for the formation of a cova- lently connected ring-structure. This reaction enables step polymerizations and cross-linking reactions together with a thermally reversibility and is therefore ideally suited for thermally stimulated polymer repair and po- tentially, recycling. Mostly, but not exclusively, the reac- tion between furane and maleimide derivatives is used for the generation of a thermally reversible bond. This has been applied already in 1969 for the synthesis of reversibly cross-linked networks, which yielded a tough rubbery film at 100ºC and returned to a re-mouldable polymer at 140ºC [30]. Subsequently, this principle has been further developed and the suitability of the system for self-healing bulk materials demonstrated [31-33]. These thermally reversible bond (cross-link) formations leading to self-healing properties upon thermal stimula- tion using the Diels-Alder reaction (see Scheme 1) can be used in application areas like coating systems [34]. Using this concept, powder coatings can be applied in their cross-linked state, which has distinct advantages with respect to their storage stability. When heated above the threshold temperature flow should be sufficient to enable proper film formation. As soon as the surface is of sufficient quality, cross-linking can be started―sim- ply by cooling down! In a fully cross-linked state of a powder coating system, i.e., below a certain threshold temperature, the coating will exhibit its essential proper- ties with respect to mechanical strength, etc., but in its (partly) de-cross-linked state, above the threshold tem- perature, it will show a certain level of plasticity and flow. This plasticity will decrease problems in the area of film formation of powder coatings, will enable repair of the coating using their self-healing properties (see Figure 5). Scheme 1. Schematic representation of the Diels-Alder reac- tion used for thermally stimulated repair. Figure 5. Visualisation of the self-healing of a cross-linked powder coating based on the acrylate copolymers: a) crosslinked powder, b) molten powder, c) damaged coating, d) re-flow, e) repaired coating [34], scale bar = 5 mm.
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 879 Besides application in coatings [35-38], reversibly cross-linkable materials are of interest for several areas of applications including thermally reversible bonding [39], thermally reversible solubility of polymers [40], processes connected with the recycling of plastics [37], encapsulates which open at elevated temperatures, re- versible data storage medium [41] and also as matrix material in composites [42,43]. Here, polymeric materi- als with dicyclopentadiene units in the polymer back- bone were used as a matrix for re-mending composites reinforced with graphite fibers [42]. The graphite fibers are used as electrical conductors to provide the necessary heat to the polymer. Microcracks, introduced by bending the substrate were healed by applying electric currents. Alternatively, arrays of conductive, electromagnetic scattering elements such as copper wires and coils were incorporated together with reinforcing fibres into a ma- trix consisting of a thermally reversible crosslinked net- worked base on a retro-Diels-Alder mechanism [43]. Since the wires are uniformly distributed within the ma- trix they can be used to heat the composite quick and uniformly by absorption of electromagnetic radiation. Furthermore, the reinforcing fibres are also contributing to the healing mechanisms, since they display a negative coefficient of thermal expansion (Kevlar: –2 to –6 ppm/K) and ensure therefore a mechanical closure of cracks while raising the temperature and increasing the healing efficiency in such a way to a great deal. In a similar way, embedded shape-memory alloy wires [44] as well as a syntactic shape memory polystyrene foam [45] have been used to improve the performance of an existing self healing system. The improvement in performance due to crack closure enables multiple self- healing actions and increases crack fill factors during the repair action. Non-covalently bonded polymeric systems are also known to heal upon thermal treatment. For example a supramolecular network can be established by thermally reversible H-bonds leading to rearrangements of the molecules in the non-bonded, heated state and reforma- tion of the network in the “cold” state [46,47]. A reversible formation of ionomeric “cross-links”― clusters, which are formed by phase separation of the charged parts of macromolecules from the neutral chain segments can be used also as a self-repair mechanism being repeatable many times depending primarily on the stability of the polymer. Although it is not an autonomic process, it is activated when thermal energy is trans- ferred to the polymer. During high-speed impact, energy is absorbed which is elastically stored and dissipated as heat. This increases the local temperature of the im- pacted polymer above the melting point (disrupting the physical cross-links) while having little effect upon the temperature of the surrounding matrix. The ionic do- mains persist in the melt so that the polymer can be elongated to high levels of strain and rebound elastically when the stored energy is released at failure. The level of stretching enables the polymer to seal the cavity as it returns to its original position, but it is the viscoelastic properties and the capacity of physical cross-links to reform that determines the final level and strength of healing. The structural integrity of the polymer provides sufficient strength in the melt to prevent other deleteri- ous effects from polymer flow [48,49]. 3.2. Non-Thermal Stimulation of Self Repair In a similar manner to the retro-Diels-Alder compounds, reversible cross-links can be established by photo in- duced cross-linking, which can be reversed by irradia- tion with a different wavelength to heal cracks, such as with cinnamic acid derivatives [50]. A covalently cross-linked network containing ally sul- fides is able to undergo photomediated, reversible cleavage of its backbone to allow chain rearrangement for rapid stress relief at ambient conditions without me- chanical property degradation [51]. The key to this re- versible backbone cleavage is addition-fragmentation chain transfer. A reaction diffusion of radicals through the cross-linked matrix occurs initially by reaction of a radical with an in-chain functionality, forming an inter- mediate, which in turn fragments, reforming the initial functionality and radical. This addition-fragmentation process alters the topology of the network, but the poly- mer chemistry and network connectivity remain un- changed. Alternatively, also an electrical current run through a conductive material system may be used to assist healing [52]. By imparting conductive properties into these ma- terials, one may obtain ‘real-time’ status of a material’s structural integrity through electric feedback mecha- nisms. This feature could lead to new approaches for detecting and quantifying microcracks which further could lead to materials capable of recording their stress/load histories. Other possibilities include using electric fields or currents as healing function. Upon the formation of a microcrack, the total number of electron percolation pathways within the material should de- crease. As a result, its inherent electrical resistance should increase accordingly. If the material is integrated into a circuit, the drop in conductivity could be used to trigger a simultaneous increase in the applied electric field. Considering that the microcrack is the source of the increased resistance, this voltage bias should result in the generation of heat localized at the microcrack. By harnessing the generated thermal energy to overcome kinetic barriers, the system may be electrically driven
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 880 back to its original (i.e. a low resistance/high-current) state. This has been shown using N-heterocyclic carbines and transition metals [52]. It is well known that “crack healing” of polymers is observed via stimulation using a specific solvent. This phenomenon is called “solvent healing”. In this healing process, the solvent is applied onto the fractured poly- mer until healing has occurred and then removed. The observed crack healing is a superposition of two differ- ent mechanisms: firstly, the formation of a close contact of the crack surfaces initiated by internal compression induced by surface swelling, and secondly, the self-dif- fusion of polymer chains across the interface forming the physical links (entanglements) between polymer chains coming from different sides of the interface promoted by the action of the solvent lowering locally the Tg [53,54]. This concept can also be used for a built-in self-healing system, as described below. 3.3. Synthetically Designed Autonomously Self-Repairing Systems 3.3.1. Ceramic Systems An existing self-healing material or system can be found in the layers applied in barrier systems (liners) to ensure security of deposits of dangerous waste. Here, geo-syn- thetic clay liners (GCLs), which contain natural sodium bentonite encapsulated between geo-textile components, are the sealing elements [55]. Desiccation cracks, which cause a significant increase of the permeability, can be repaired by the self-sealing properties of calcium and sodium bentonite. Alternatively, self-healing sealing elements based on the principle that two or more parent materials (for ex- ample pozzolanic material and lime containing material) placed in vertical or horizontal layers, are described. These materials will react at their interfaces to form in- soluble, barrier reaction products and heal themselves after being fractured (see Figure 6 [56]). Curiously, the same strategy has been operating in the construction for centuries. Many ancient Roman con- structions made from limestone survived only because of the self-healing capacity of limestone in interaction with moisture/water. The phenomenon of self-healing in con- crete has been known for many years [57-62]. Cracks in reinforced concrete are unavoidable and the corrosion of reinforcing steel due to de-icing salts or sea water is a major course of deterioration of reinforced concrete structures while disrupting the naturally formed corro- sion protective passivation film. It has been observed that some cracks in old concrete structures are lined with white crystalline material suggesting the ability of con- crete to self-seal the cracks with chemical products (CaCO3), most likely with the aid of rainwater and car- bon dioxide (see Figure 7). The healing of cement re- sults in the voids being filled with hydration products which have a bulk volume approximately 2.1 times the original volume [63], an effect which is discussed below. However, efficient self-healing occurs only for cracks not exceeding a certain width (ca 135 microns) [64]. Unfortunately, this mechanism not always work in normal concrete because the width of the tensile cracks cannot be easily controlled or tuned. Localized fracture leads to continued increases in crack width under de- creasing tensile load, and rapidly exhausts the amount of chemicals available for crack sealing and composite re-healing. Thus, it is critical that the tensile crack width is controlled and must be limited to a few tens of mi- crons. Again, the success of the repair action depends Figure 6. Schematic illustration of the self-sealing/self-healing feature of a pozzolanic and lime containing barrier material system: a) before fracture; b) after fracture. Reprinted from Waste Management, Laboratory development and field demonstration of self-sealing/self-healing landfill liner, 25, C. Shi, R. Booth, 231-238, Copyright (2005), with permission from Elsevier.
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 881 strongly on the damage degree accumulated. When the damage degree is less than the threshold, the self-healing ratio of concrete is increased with the increase in dam- age degree; once the damage degree exceeds the thresh- old, the self-healing ratio is decreased with the increase in damage degree [65]. In recent years, fiber-reinforced cement-based com- posites optimized for ultra high tensile ductility with a minimized amount of fibres have been designed based on micromechanics design tools [66]. Such materials, defined as Engineered Cementitious Composites (ECC), display “plastically yield” under excessive loading through controlled micro-cracking while suppressing brittle fracture localization and thus enabling self-repair actions. The potential of calcite-precipitating bacteria for con- crete or limestone surface remediation or durability im- provement has only recently been investigated and is a possible alternative to repair cracks in concrete [67]. In the case of composite materials, it is also possible to use an inorganic phase to perform the self-repairing process, as demonstrated in the case of decalcifica- tion-hydration reactions of hydraulic (CA) fillers in poly-phenylenesulfide (PPS) coatings used in geother- mal applications. The hydraulic fillers, which can heal and repair micro-sized cracks appearing on the surfaces of corrosion protection coatings, are embedded into the matrix material (PPS) [68]. The decalcification-hydra- tion reactions of the CaO-Al2O3 and CaO-2 Al2O3 reac- tants present and exposed in the cracks lead to the rapid growth of boehmite crystals, densely filling and sealing the cracks, while the calcite leaches out of cracks be- cause of the formation of water-soluble calcium bicar- bonate (see Figure 8). Healing and repairing of micro-sized cracks generated on the surfaces of the PPS coating was observed after exposure of the cleaved coatings to a simulated geo- thermal environment (200°C, CO2-loaded brine). During exposure for 24 h block-like boehmite crystals (ca. 4 m in size) filled and sealed the open cracks. This was re- flected in an increase in pore resistance up to two orders of its magnitude compared with that of cleaved coatings without fillers [68]. 3.3.2. Viscoelastic Recovery and Healing Micro-damage self-healing also exists in asphalt mix- tures. After the removal of external load, two processes occur: the first is viscoelastic recovery in the bulk of the material and the second is healing in a fracture process zone [69]. Viscoelastic recovery occurs in the bulk of the material only after a stress or strain is induced which is sufficiently large to generate damage. The phenomenol- ogical difference between viscoelastic recovery and healing is that the former is due to the rearrangement of molecules within the bulk of the material, whereas the latter is due to the wetting and inter-diffusion of material between the two faces of a micro-crack to achieve prop- erties of the original material. The three primary steps in the healing process are: 1) Wetting of the two faces of a micro-crack 2) Diffusion of molecules from one face to the other 3) Randomization of the diffused molecules to reach the level of strength of the original material Again, especially rest periods introduced at certain damage levels increase the fatigue life of asphalt binders [69]. A very recent example of self-healing via reformation of weak, fracture interrupted bonds has been demon- strated on a supramolecular rubber employing molecules that associate together to form both chains and cross- links via hydrogen bonds [70] (see Figure 9). By mixing ditopic and multitopic molecules, which are able to associate with more than two other molecules, a network could be formed. The system shows recover- able extensibility up to several hundred per cent and very little creep under load. In contrast to conventional cross-linked or thermo-reversible rubbers, these systems, when broken or cut, can be simply repaired by bringing together fractured surfaces in contact―an example of autonomous self-healing at room temperature. The process of breaking and healing can be repeated many Figure 7. Crack blockage in mortar specimen by CaCO3 after NaCl solution exposure, crack width = 49 microns. Reprinted from Cement and Concrete Research, Permeability and self-healing of cracked concrete as a function of temperature and crack width, 33, H.-W. Reinhardt, M. Jooss, 9131-9136, Copyright (2003), with permission from Elsevier.
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 882 Figure 8. Self-repair action of a decalcification-hydration reaction on a polymer composite surface [68]. Figure 9. Schematic view of the Supramolecular reversible network formed by mixtures of ditopic (blue) and tritopic (red) molecules associated by directional H-bonds (represented by dotted lines) as employed for the self-healing rubber. Reprinted by permission from Macmillan Publishers Ltd: [Nature] (Self-healing and thermoreversible rubber from supramolecular assembly, P. Cordier , F. Tournilhac , C. Soulie-Ziakov, L. Leibler, 451, 977-980), copyright (2008). times. However, the time needed to establish a contact of the fractured surfaces determines the healing efficiency. Longer healing times lead to better healing, but even when contact time is as short as fifteen minutes a re- paired sample can be deformed up to about 200% with- out breaking. In order to be self-mending, the supramolecular rub- ber has to be made from small molecules and the su- pramolecular associations have to be strong and long- lived so that at equilibrium, the fraction of non-associ- ated groups in the network is low. However, the strength of the associations has to be lower than that of covalent bonds so that, when broken, many non-associated groups are present near the fracture surface. Self-healing is effi- cient because a large number of groups ‘eager’ to link is available. At shorter healing times, fewer bridges across the interface are formed and the elongation at break is lower. When the sample is not mended immediately after being broken, the number of non-associated groups available for healing progressively decreases as they find other partners for H-bonds and become unavailable for a re-formation of the entangled network. 3.3.3. Self-Healing by Phase Changes and Volume Expansion The self-healing potential in metals and metal alloys is connected with a dynamic precipitation of atoms and the consequent potential to delay crack initiation and crack propagation as observed in Al alloys similar to a plastic- ity-induced crack closure. When a dislocation interacts with a precipitate, solute atoms will be transferred to the precipitate, causing Ostwald ripening, if their binding energy to the precipitate exceeds that to the dislocation. Conversely, solute atoms will be removed from the pre- cipitate if their binding energy to the dislocation is greater. Dynamic precipitation tends to compensate for micro structural damage, with the result that a higher integrity structure is maintained for an extended lifetime [71]. Alternatively, the precipitation of dissolved atoms like B and N under formation of BN on creep cavity surfaces (in for example austenitic steel) leads to a self-healing of the creep cavitations together with an increase in creep rupture strength and ductility [72]. 10 m 10 m
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 883 Oxidative self-recovery of surface damaged ceramics and ceramic composites may also be a useful self-repair mechanism (Figure 10). Oxidation of NiAl/α-Al2O3 composites provides the metamorphic surface layers consisting of NiAl2O4 and Al2O3 with compressive stress to improve the mechanical properties [73]. The peculiar- ity of this material is the dominant formation of NiAl2O4 along with the grain boundary of the matrix Al2O3 by the reaction, 232 24 2NiAlAlO(boundary)5/2O2NiAlO The rapid diffusion of the reaction product through the grain boundary results in the repair of surface defects (see Figure 10). This concept has been further developed for thermal barrier coatings with a composition of NiCrAlY, again with Al as reactive element. This enables a reaction with oxygen to form a protective barrier layer under volume expansion in response to damage due to thermal mis- match during thermal cycling. Here, an addition of 0.1- 0.2% Zr leads to an optimisation of the self-repair proc- ess [74]. Similar concepts were reported for the systems ZrB2/SiC [75], SiC/Al2O3 [76], SiC/Si3N4 [77], BN/SiC, B4C, SiC/B4C, MoSiC2 containing ceramics and Ti3AlC2 [78], where the surface crack oxidation leads to an effec- tive volume expansion and, thus, to a filling of the crack opening. Volume-expanding phases are of course most suited to be applied in self-healing systems, since they offer the possibility to fill the empty crack volume completely and to re-generate the structural integrity of the system. This requires a material identically or similar in properties to the damaged matrix material. Examples include phase transition tetragonal-monoclinic (e.g. in ZrO2) phase transitions, phase transitions as seen in sulphur, TRIP transformation, piezo-effects, curie-transitions and others which induce a volume change of 1-4%, sufficient to fill cracks and to perform a healing operation. Those changes are mostly triggered by a critical strain or/and by temperature. More simply is the healing of zirconia and especially yttria-stabilized zirconia (YSZ) where an efficient damage recovery in large-scale molecular dy- namics simulations has been observed [79]. Dynamic annealing is highly effective in zirconias during the first 5 ps of damage evolution, especially in and due to the presence of oxygen structural vacancies. The number of anion displacements in YSZ keeps increasing with time instead of reaching a steady value as in ZrO2. This dem- onstrates the role played by structural vacancies in the migration of O2-. Defect diffusion plays an importantrole in the dynamic recovery of radiation damage. Espe- Result of the crack healing: Damaged structure Repaired structure Figure 10. Crack healing of ceramics due to oxidative self-recovery of ceramics [73]. Flexural strength (a) without defect, (b) with defects, (c) annealed, (d) repaired, (e) removal of defect, (f) oxidized without defect, and (g) oxidized after removal and fracture sur- face of (A) with defects and (B) repaired materials, the symbol o corresponds to the right axis. 30 m 200 m 2 m 30 m 2 m
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 884 cially in YSZ, the anion interstitials almost completely annihilate with structural vacancies, resulting in no re- sidual radiation-induced defects on the anion sublattice (see Figure 11). This results in near-complete recovery of damage. Damage recovery on the cation sublattice is assisted by the anion sublattice recovery, which explains the re- markable radiation tolerance of stabilized zirconia. If those concepts are not applicable, a possible reac- tion with components provided by the environment us- ing transport via the gas phase might be an option for a self-repair action. This principle is especially useful in coatings where dimension constraints prevent the use of other options for self-repairing design (see below). Coatings should not only protect a surface from a possi- ble damage and/or corrosion but should also provide additional properties like anti-reflection, gas barrier etc. However, if coatings are damaged and/or pinholes formed, serious damage could occur due to corrosion on and in the substrate. To fill such damage areas and/or pinholes and to restore the passive corrosion protection or other functionalities, the coating can be loaded with nanoparticles, which react upon volume expansion with moisture or oxygen. In a practical example, raw smectic clay has been used as the phase being able to absorb moisture under volume expansion [80]. In a later study, this concept has been developed further leading to a true recovery of damaged surfaces [81]. There, the option of healing surface scratches in multi layer coatings consist- ing of a polysiloxane film on top of a thin montmorillo- nite layer as expandable phase was studied (see Figure 12). Filling of cracks in the polymeric topcoat occurred primarily within the first two hours of exposure to mois- ture-saturated air and resulted in a good restoration of the surface flatness [81]. 3.3.4. Mimicking Nature Mimicking nature has resulted in a variety of self-heal- ing systems. One of the first synthetically design sys- tems developed, tested and used in ceramics (concrete) and subsequently in polymeric matrices compromising all three functionalities (damage sensor, healing mobile materials, structurally integer functioning system) are resin filled glass capillaries incorporated in the matrix material [82-90]. Upon damage or fracture, the glass capillaries act as a strain sensor, releasing the encapsu- lated adhesive components (epoxy and hardener, cyanoacrylate etc.) into the composite structure to per- form the repair action while (partially) filling the crack. The damage can be sensed/visualized by adding a fluo- rescent dye to the components (see Figure 13); the cap- sules (glass capillaries) also serve as part of the (rein- forcing) composite structure. This ‘bleeding composites’ approach thus combines damage detection with a high sensitivity due to the con- tinuity of the hollow fibres and self-repair, however, also with two draw-backs: 1) they will release an excess of healing liquid since the volume of the compartments is often much larger than the damage volume and 2) they will display a tendency to clotting since the propagation of the repairing reaction of the stored agent within the hollow fibre can still occur thus preventing the chance of multiple repair. Systems following a similar idea were developed for an application in thermosets (epoxy); the approach has been applied to other matrix materials as well [91-94]. Here, the resin containing containers are hollow poly- meric capsules (see Figures 14,15). The fragile capsules act as sensor and as reservoir of the resin. Upon fracture the released monomer reacts with the catalyst distributed within the matrix forming a cross-linked polymer network and repairing the damage. Figure 11. Evolution of the number of interstitials in YSZ and pure ZrO2 following 30-keV Zr recoils. The numbers of cation and anion interstitials in ZrO2 and YSZ peak at about 0.2 ps and then decline sharply. Subsequently, in YSZ, the anion in- terstitials almost completely annihilate with structural vacan- cies, resulting in no residual radiation-induced defects on the anion sublattice. The difference in anion sublattice damage between ZrO2 and YSZ is due to the presence of structural vacancies in YSZ. (squares, triangles, and diamonds represent [001], [110], and [111] recoils, respectively) and pure ZrO2 (circles) [79]. (a) (b) Figure 12. Crack-healing of multilayer coatings due to phase expansion upon moisture absorption before (a) and after 21 h of healing (b) in wet atmospheric conditions [81]. Scale bar = 10 microns.
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 885 The healing efficiency of this concept is high (see Fig- ure 16) [95-97]. However, since a significant load of microcapsules is required to get efficient self-healing due to the small Figure 13. Fracture of a hybrid solid/hollow fibre reinforced plastic showing bleeding of UV fluorescent dye along crack paths(x 45 magnification) [88]. Figure 14. Schematic picture of the self-healing action of a in spherical capsules embedded resin upon damage/fracture of the matrix material. Reprinted by permission from Mac- millan Publishers Ltd: [Nature] (Autonomic healing of polymer composites, S. R. White, N. R. Sottos, P. H. Geu- belle, J. S. Moore, M. R. Kessler, 409, 794-797), copyright (2001). Figure 15. SEM picture of a broken capsule. Reprinted by permission from Macmillan Publishers Ltd: [Nature] (Auto- nomic healing of polymer composites, S. R. White, N. R. Sottos, P. H. Geubelle, J. S. Moore, M. R. Kessler, 409, 794- 797), copyright (2001). (a) (b) Figure 16. a) Healing efficiency of the capsule strategy in a single experiment and b) in time [95]. amount of liquid depleted upon fracture and the limited probability of fracture during damage, the mechanical (m) η=90.3% 20(m)
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 886 properties of the matrix material are substantially weak- ened and limit the application of this concept. Further- more several material processing aspects are also not favourable. Anyway, these systems have been further developed and optimized for coating applications [98-101] since they offer an autonomic self-repair for anti-corrosion protective coatings. The latest developments of autonomous systems com- bine the concept of the incorporation of a self-healing liquid with the increase in mobility of macromolecules via solvent stimulation [102-104]. Here, solvent-con- taining micro-capsules were either embedded in an ep- oxy matrix or in a matrix of thermoplastic polymers. In the case of the thermoset, the presence of the solvent increases the mobility in the system and healing effi- ciencies of up to 82% was observed due to molecular diffusion and reaction of residual functionality [102, 103]. The healing performance appears to be inversely related to cross-link density. Healing with epoxy-solvent microcapsules is superior to capsules that contain sol- vent alone (up to 120% healing efficiency), and data showing multiple healing events are reported for this system. In the case of the thermoplastic matrix, the mo- bility of the macromolecules increases due to the lower- ing of the glass transition temperature via solvent chain interactions leading to the possibility of re-entanglement formation and complete crack closure (see Figure 17) [104]. In order to combine the advantages of the two existing concepts for the storage of a self-healing liquid (the hol- low fibre container and the spherical capsule concept), experiments have been carried out to develop anisotropic capsules [105]. Such particles offer a better probability of being fractured upon damage than spheres. Thus a substantial lower load of capsules (up to five times less) is needed for a realisation of self-healing properties and the initial mechanical properties of the system will be preserved [105]. On the other hand, they offer the same advantages with respect to processing and preparation as the spherical capsules compared to the hollow fibres. Ultimately, a mimic of the blood vessel system capa- ble of a repeated, autonomic repair of damaging events seems a perfect self-healing material system. Healing in such systems is accomplished by a vascular network system supplying the necessary components at the dam- age site. A vascular system permits a continuously and repeatable repair of all types of failure modes at any point in the structure since it renews the supply of the healing part of the system during the lifetime of the structure at any location and any time. A skin structure exhibiting flexibility, self-healing and damage sensing is the simplest system realizing a net- work-like supply of an active self-healing liquid [106]. The skin is fabricated on a substrate of copper-clad polyimide sheets in a layer-by-layer technique using polyimide sheets and an ultraviolet (UV)-curable epoxy. The UV-curable epoxy is used as both a structural adhe- sive and as the self-healing fill material (see Figure 18). The skin structure is integrated with an array of induc- tor-capacitor (LC) circuits, where each circuit is charac- terized by a unique resonant frequency. If the skin is damaged, the UV-curable epoxy is released and is cured by ambient sunlight. Further, damage affects one or more of the LC circuits, altering its resonant frequency. An integrated antenna coil is used to detect and locate the damaged portion of the skin; so far tests indicated a good performance with respect to self-healing of the skin and fault isolation. Other examples of such a system have been described by Toohey et al. [107,108] and by Williams et al. [109, 110]. Here, a 3-dimensional micro-vascular network system, either manufactured by a direct write assembly procedure using a fugitive ink or by connection of glass capillaries via risers has been embedded in an epoxy Figure 17. MRI tomogram of a healed thermoplastic contain- ing solvent filled capsules. The green capsules are empty. The majority of the empty capsules are located at the fracture plane as intended, healing is obtained, and no empty space of the original fracture plain is observable [104]. Figure 18. Basic diagram of self-healing skin, top view with cutaway and cross-section. Reprinted by permission from IOP Publishing Ltd: [Smart Mater. Struct.] (A flexible, self-healing sensor skin, J. A. Carlson et al, 15, N129), copyright (2006).
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 887 matrix system and tested upon bending. These systems show repeatedly crack healing upon damage. Alternatively, 3D microvasular networks can be real- ized simply by loading the hollow micro-fibres of a free-standing paper manufactured by electro-spinning with a healing agent displaying a rapid reactivity, vola- tility and ability to propagate repair triggered e.g. by the influx of moisture [111]. The self-healing agent used is Ti Cl4 blocking the pores of the hollow micro-fibres as well as sealing possible cracks by the formation of ce- ramic particles of TiO2 after hydrolytic decomposition in contact with water vapour. The natural blood vessel system works, however, in a slightly different way [112]. In this case, a temporary repair as response of a physical damage is achieved in the form of a clot that plugs the defect. During subse- quent days steps to regenerate the missing parts are initi- ated. The healing of a skin wound is a complex process requiring the collaborative efforts of many different tis- sues and cell lineages. Inflammatory cells and then fi- broblasts and capillaries invade the clot to form a con- tractile granulation tissue that draws the wound margins together; meanwhile, the cut epidermal edges migrate forward to cover the denuded wound surface. The for- mation of a clot then serves as a temporary shield pro- tecting the denuded wound tissues and provides a provi- sional matrix over and through which cells can migrate during the repair process. The clot consists of platelets embedded in a mesh of crosslinked fibrin fibers derived by thrombin cleavage of fibrinogen, together with smal- ler amounts of plasma fibronectin, vitronectin, and throm- bospondin. An interesting analogy to the process uses nanoparti- cles dispersed in polymer films and shows in simulations and experiments a preferred coagulation of nanoparticles at areas of stress concentration similar to the clotting of blood platelets at zones of damage [113-116]. This is because the mobility of the filler particles at the length scales present in nanocomposites is controlled by the conformational entropy of polymer chains. Polymer chains close to nanoparticles are stretched and extended, which results in an entropy penalty. This decrease in polymer conformational entropy is greater than the de- crease in nanoparticle translational entropy; thus, nanoparticle-polymer interactions are minimized by segregation of the nanoparticles in areas of stress con- centration such as a crack tip. For particles comparable to the radius of gyration of the polymeric chain, the de- crease in conformational entropy of the respective polymer sub-chains upon particle sequestration is domi- nant; the chains gain conformational entropy while re- pelling the particles because they do not have to stretch around particles [113-115]. The system can relieve the entropic cost of chain stretching by allowing the parti- cles to self-assemble to the solid walls. In the presence of a notch, the nanoparticles are driven to localize in the notch. The driving force for this localization is a poly- mer-induced depletion attraction; the confined polymers in the melt gain conformational entropy by “pushing” the fillers to the surfaces and into the notch (Figure 19). The time required for the particles to migrate to the notch is comparable to the time needed for the chains to move by approximately four radii of gyrations. The morphology obtained from the simulation allowed a de- termination of the mechanical properties of the nano- composite-coated surface. The calculations show that the nanoparticle fillers significantly reduce the stress con- centration at the notch tip relative to the case where the notched surface is just coated with a pure polymer layer (see Figure 20). As a consequence, load transfer from the matrix to the agglomerated nanoparticles is predicted and the me- chanical properties can recover to 75% of their original value [114]. The calculations on the crack tip opening displacement indicate that the presence of the nanocom- posite in the notch would inhibit the system from un- dergoing further damage (crack propagation from this notch) when an external load is applied to the system. It is important to realize that some fractions of the polymer are also localized in this damaged region. If the macro- molecules and the particles are chemically compatible, the chains provide cohesion between the fillers and the polymer coating. The application of such nanocomposite coatings could thus constitute an important step in the production of components with defect-free surfaces. Upon appearance of a defect, the coating effectively senses its presence and then causes the repair of the damaged area. In a practical example, nanoparticles are added to a high viscous liquid polymer that is sandwiched between two brittle, glassy layers (see schematically in Figure 21). This architecture is common in multi-layer composites that are used in optical and anticorrosion coatings, mi- Figure 19. An instantaneous molecular configuration showing a surface notch filled with nanoparticles due to a depletion attraction between the particles and the surface. Particle beads are shown as spheres and polymer chains as lines [115].
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 888 Figure 20. Results of the calculation of the stress distribution using a lattice-spring model for (a) a polymer coating not con- taining nanoparticles. The stress reaches a maximum at the notch tip. (b) The polymer coating contains nanoparticles and the stress at the notch tip is significantly reduced. The colour bar indicates the magnitude of the stress [114]. croelectronics packaging, and solid-state devices. Such films are susceptible to failure through the formation of cracks, which propagate vertically to the polymer layer. Since the polymer is fluid-like it expels the nanoparticles to the brittle surfaces, where some of the particles pack into the cracks, effectively mending the brittle surface. In the experimental study [117], the particles were fluo- rescent and could readily be visualized in the cracks (see Figure 22). In this example, the polymers and particles provide the healing mechanism without any external intervention. Figure 21. Scheme of a multilayer composite (coating). A polymer layer (represented by the black chains) containing nanoparticles is sandwiched between two intact, brittle layers. Upon appearance of, a crack in the top surface and due to the particle-polymer interactions, the particles become localized in the crack and effectively mend the damage. Figure 22. Fluorescence microscope image of a crack in a 60 nm SiOx layer on a mixture of PMMA with PEO-covered 3.8-nm-diameter CdSe/ZnS nanoparticles. The cracked film is viewed with a fluorescence microscope, in which the segrega- tion of the CdSe nanoparticles to the cracks is highlighted by the fluorescence of the nanoparticle. [117], scale bar = 50 mi- crons. Reprinted by permission from Macmillan Publishers Ltd: [Nature Materials] (Entropy-driven segregation of nanoparti- cles to cracks in multilayered composite polymer structures, S. Gupta , Q. Zhang , T. Emrick, A. C. Balazs, T. P. Russell, 5, 229-233), copyright (2006).
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 889 The approach has the advantage of being “re-usable”; when new cracks appear, the polymers again drive the particles to the damaged site and thereby continue the repair. In principle, this process can continue until essen- tially all the particles in the polymer layer are expelled and localized in the cracks. Finally, since the particles can potentially be made out of the same materials as the brittle walls, the system will resemble the initial, undamaged materials. Additionally, the fluorescing particles provide a useful diagnostic tool, pinpointing the location of the cracks and revealing the mechanical state of the material. A model has been published describing the rolling motion of a fluid-driven, particle-filled microcapsule along a heterogeneous, adhesive substrate to show how the release of the encapsulated nanoparticles can be har- nessed to repair damage on the underlying surface [118]. The microcapsules that could act as ‘artificial leuko- cytes’ are driven by an imposed flow to move along an adhesive surface, which represents the wall of a micro- channel (either in the synthetic microvasculature, or more generally, in a microfluidic device). The micro- capsules enclose a solution of nanoparticles and these nanoparticles can diffuse from the interior of the capsule into the host fluid. When the capsule is trapped at the leading edge of the damaged region, a relatively high fraction of the released particles are now localized near this region and can more effectively cover this damaged site. Once the damage is repaired, the capsule can again be driven by the imposed flow to move along the surface where they could potentially sense and perform the re- pair action at another damage site. So far, all self healing mechanisms and discussed sys- tems tried to mimic nature by filling or re-filling cavities of damaged materials just like it is the case in nature. However, nature has more than one strategy to deal with threads. Continuously re-shaping, metabolic cycles as well as isolation of sub-critical thread concentrations (bacteria) are also healing strategies in nature. Such metabolic reactions can also be used in poly- meric systems to accompany a self-healing process as described for polycarbonate (PC, polyetherketone (PEK) and poly-p 2.6 dimehylphenylenether (PPE) [119]. In the last case e.g., the polymeric chains cut by heat, light, oxygen and external mechanical force will produce a radical on the end of the scission chain in the first step. Subsequently, a hydrogen donor stabilizes the radical. The Cu (II) catalyst added beforehand forms a complex with each end of the two different chains and withdraws two electrons from them. The chains combine, eliminat- ing two protons from the ends and reducing the copper Cu (II) to Cu (I). The Cu (I) migrates in the polymer and reacts with an oxygen molecule in an oxidation step to Cu (II). The oxygen ion then reacts with two protons to form a water molecule which leaves the system. Key factors for the speed of the self-repair action are the concentration of the chain ends and the mobility of the chains (the recovery rate increases with decreasing ini- tial molecular weight and increasing amount of dimeth- ylphthalate as plasticizer), the oxygen partial pressure in the surroundings and the speed of emission of water (see Figure 23) [119]. The isolation of subcritical damage and the stop of further growth is the strategy applied while introducing Figure 23. Scheme of the self-repairing metabolism in PPE. Reprinted by permission from IOP Publishing Ltd: [Sci. Tech- nol. Adv. Mater.] (Self-repairing mechanism of plastics, K. Takeda et al, 4, 435), copyright (2003). Figure 24. An illustration of S segregation and BN precipita- tion on creep cavity surface [120]. Grain boundaryCreep cavity S segregation (MP:112.8℃) Grain boundaryCreep cavity BN B N BN precipitation (MP:3000℃) S S
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 890 self-repair to austenic stainless steel [120] (see Figure 24). High temperatures during use of austenic steels leads to low ductility creep fracture in long timescales caused by the nucleation, growth and coalescence of grain boundary cavities. Dissolved sulphur segregates on cavity surfaces easily, and enhances the creep cavitation remarkably most likely due to a lowering the creep cav- ity surface energy and increasing the surface diffusion rate. The additions of Ce (0.016 wt%) is highly effective in removing the traces of soluble S in the steel through the formation of Ce2O2S. In the absence of S segregation, B (0.07 wt%) and N (0.007 wt%) can segregate due to their small atomic diameter efficiently to the creep cav- ity surface and form boron nitride (BN) compound on the surface during creep. As BN is very stable at high temperatures, the precipitation of BN film on the creep cavity surface suppresses the creep cavitation in steel by reducing the creep cavity growth rate. The BN precipita- tion continues during creep exposure and heals the creep damage. The creep cavities are self-healed by a con- tinuous precipitation of BN on creep cavity surface dur- ing creep exposure, and the growth of the self healed creep cavities is suppressed almost completely. The function of self-healing for creep cavitation provides the steel with a longer rupture life and higher rupture ductility. 4. SENSORS AND TRIGGERS FOR SELF-HEALING SYSTEMS Fundamental to the understanding and implementation of self-healing systems is the detection of damage and a trigger mechanism which initiates the repair action. This is done in nature efficiently e.g. in the case of wound- healing by growth factors and matrix components that are available to provide these “start” signals, triggering relatively sedentary cell lineages at the wound margin to proliferate, to become invasive, and then to lay down a new matrix in the wound gap [112]. However, the tricky part is really the distinction be- tween the healthy and the damage status of a given sys- tem. Here, a decision between acceptable damage and unacceptably changed behaviour of the system has to be made, or in other words an indication of the time of the usual transition from a normal state to a degraded state when attacks become successful and/or faults begin to take effect. In the end, any system should detect failure in a timely manner and must be smart enough to com- pute the degree of malfunction in the system and to asses finally whether the system actually needs the interven- tion by a “recovery program”. As stated above, sensor elements are essential for the design and functionality of self-healing systems. In the case of the hollow glass capillaries or the urea-formal- dehyde capsules used for the storage and delivery of a liquid performing the self-healing action, the shell of the capsule or the glass capillary itself act as strain sensor. They are tuned by their mechanical properties to break and to release the fluid in the event of damage. The self-healing system based on re-formation of co- valent bonds during a heating-cooling cycle fulfils in itself the sensor function. The low viscous system bridges the gaps of crack or damage due to the surface tension properties of the liquid. However, it is certainly preferable to get access to autonomic self-healing systems with a more sophisticated embedded structural health monitoring sensor unit ena- bling decision making about the place and time of the required repair action to be taken. There are a number of possible damage sensors available, which are discussed with respect to their advantages and performance in [121]. Most important is the size and/or the location of the damage that can be resolved by a certain sensor sys- tem (see Figure 25), the size of the sensor itself and the requirements to get a certain sensor functioning (power consumption). A combination of vibration and wave propagation data has been used to determine the location and degree of damage in structural components in an automated dam- age identification technique requiring minimal operator intervention [122]. To build such a detection system, a structure had to be instrumented with an array of actua- tors and sensors to excite and record its dynamic re- sponse. In order to determine structural damage, a dam- age index, calculated from the measured dynamic re- sponse of the structure in a reference state (baseline) and the current state, was introduced. While the vibration-based analysis was used to iden- tify widespread damage within the structure, the analysis of the waveform signals provides detailed information on the location and nature of smaller defects. The unified computer-assisted automatic data analysis procedure can improve the reliability of the defects detection capability and aid in the development of in-situ health monitoring systems for defects-critical structures. In a similar way, electrical resistance measurements are applied to moni- tor the health situation of a certain system using a (per- colated) conductive network or carbon fibres incorpo- rated in a structure. The resistance changes irreversibly upon damage, as shown for damage inflicted by flexure, tension, fatigue, and impact. The oblique resistance, as measured at an angle between the longitudinal and through-thickness directions, is particularly sensitive. This enables the real-time monitoring of damage in form of fire breakage and delamination in the case of compos- ites tested in tension fatigue, compression and impact and provides an estimate of the remaining fatigue
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 891 Figure 25. Sensor selection space comparing size of detectable damage with sensor size for various sensing methods [121]. life-time [123]. Also, carbon nanotube networks have been employed for sensing of distributed strain and damage and conse- quently for lifetime prediction and initiation of healing [124,125]. Under static load, changes in resistance with deformation and the initiation of microcracking during loading of the composite laminate can be monitored (see Figure 26). On unloading, the resistance decreases to nearly the original value as the transverse cracks were closed by the stiff outer plies of the composite system. Upon re- loading, the specimen show a sharp increase in resis- tance at much lower levels of deformation corresponding to reopening of the microcracks, indicative of permanent damage to the composite. This approach may be useful in self-healing systems. In a recent study, the sensor possibilities of carbon nanotube networks incorporated in composite systems with respect to fatigue-induced damage was investigated with regard to impact on in-situ health monitoring, damage prognosis and the success of self-healing [126]. Monitoring of the volume and through-thickness resis- tance enabled a determination of the extent and propaga- tion of fatigue-induced damage such as crack and de- lamination growth in the vicinity of stress concentrations. The conductive nanotube network also provides oppor- tunities to repair damage by enabling fast heating of the crack interfaces; up to 70% recovery of the strength of the undamaged composite has been achieved. Again, the repair action has been taken by an enhanced mobility of a resin at temperatures above Tg. Anyway, the first step to autonomic self-repair is cer- tainly structural health monitoring. Since all materials contain inherent defects, the detection of existence and location of damage requires a comparison between two system states. Sensors cannot measure damage directly, features need to be extracted through data processing and in a learning process type of damage and severity of damage can be identified. Therefore, e.g. machine learning for structural health monitoring has to be applied. In general, there are two approaches to damage identification [127]. Model-driven methods establish a high-fidelity physical model of the structure, usually by finite element analysis, and then establish a comparison metric between the model and the measured data from the real structure. If the model is for a system or structure in normal (i.e. undamaged) condi- tion, any departures indicate that the structure has devi- ated from normal condition and damage is inferred. Data-driven approaches also establish a model, but this is usually a statistical representation of the system, e.g. a probability density function of the normal condition. Any departures from normality are then signalled by measured data appearing in regions of very low density. The algorithms that have been developed over time for data-driven approaches are mainly drawn from the disci-
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 892 Figure 26. Load-displacement and resistance curves for a composite system with incorporated carbon nanotubes acting as strain sensors [124]. A linear increase in resistance with load is clearly seen. Upon the initiation of microcracking there is a sharp change in the resistance. In the progression from the first initiation of cracking to ultimate failure of the composite laminate the resistance changes drastically. Thostenson, E.T., Chou, T.-W., “Carbon nanotube networks: Sensing of distrib- uted strain and damage for life prediction and self healing”, Advanced Materials, (2006) 18 (21), pp. 2837-2841 Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission. pline of pattern recognition, or more broadly, machine learning. Apart from the first step to structural health monitoring, the detection of damage including data cap- ture, feature selection as a process of amplification and discarding of redundant information and novelty selec- tion, the damage location and the damage assessment which need as additional part a network of novelty de- tectors the information is finally computed via a neu- ronal network prediction of damage severity. However, without a detailed knowledge of the underlying fatigue and e.g. fracture properties of the system it will not be possible to extrapolate to failure. 5. REQUIREMENTS AND CONSEQUENCES OF SELF-REPAIR Self-healing is, in a sense, opposite to a degradation process, which as a dissipative process is connected with the production of entropy. In 1877, Boltzmann suggested a definition of entropy using the statistical thermody- namics approach and the concept of microstates as lnSk with k as the Boltzmannis constant and as the number of microstates corresponding to a given macroscopic state of a system. Microstates are the arrangements of energy and matter in the system that are distinguishable at the atomic or molecular level, but are indistinguish- able at the macroscopic level. Any system tends to evolve into a less-ordered and thus more random macro- state that has a larger number of corresponding micro- states, and thus the “configurational” entropy S grows. All processes that lead to degradation (wear, corrosion, fatigue, etc.) often involve interactions with different characteristic length scales. For example, friction and wear involve interactions of microscale and nanoscale asperities and wear particles, capillary interactions, ad- hesion, chemical molecular bonding. In most cases, these interactions lead to an irreversible energy dissipation and, therefore, to the production of entropy. In many cases, a system can be divided naturally into several scale levels with a limited interaction between hierarchical scales. The entropy production at the macroscale can be there- fore compensated by the entropy consumption at another level. Since the entropy is an additive function and the levels of the hierarchy are separated, the net entropy can be presented as the sum of entropies associated with the structures and process at corresponding scale levels as netmacro meso nano SSS S (1) where the indices “net”, “macro”, “meso” and “nano” correspond to the net entropy, macroscale, microscale (mesoscale), and nanoscale (atomic scale) components [128]. For most applications, is the integrity of the mac- roscale structure (e.g., the absence of cracks, appearance etc.) of predominant interest whereas the mesoscale and nanoscale structure is of lower interest. The integrity of the macroscale structure may be therefore repaired or restored at the expense of the micro- and atomic scale structures. In the case of the autonomous self-healing using fluid systems as applied while using capsules or capillaries filed with a glue [82-104] excess entropy, macro S asso- ciated with the macroscale defects, such as cracks or voids is compensated by affecting the mesoscale structure, e.g., by fracture of microcapsules and the release of the fluid, which decreases the degree of order of the micro- structure and thus increases the entropy for meso S. Crack propagation is an irreversible process, because when intermolecular bonds are broken, the energy is re- leased irreversibly, so the entropy amount Scrack = KA/T is produced to create a crack with area A. The co- efficient 0 < K < 1 is the fraction of the dissipated energy Q that is consumed for the creation of the crack, whereas the rest of the energy is dissipated. The ideal state without cracks corresponds to the minimum number of micro- states and thus to the lowest possible configurational entropy. The crack can be formed in many different ways and the cracked macrostate corresponds to a number of microstates producing excess configurational entropy, macr o S. In a similar manner, when a capsule ruptures and
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 893 its content is released, the configurational entropy grows because mixing occurs. The configurational entropy growth of mixing of two substances is given by mixing1 122 ln lnSRnXnX (2) where n1 and n2 are the amounts in moles of two pure substances, X1 and X2 are mole fraction in the solution, and R is the gas constant. Part of this excess entropy can be consumed for healing the bonds at the crack. The net configurational entropy grows, however the growth is not due to the cracking but due to microcapsule rupture and an irreversible decrease of their number. If N capsules are ruptured to heal the crack with the area A, the net entropy production is given by the meso- scale entropy of mixing minus the macroscale entropy of crack healing -0 netmeso macromixing L SSS NSK T (3) In casemacro S < meso S, the healing is done by de- creasing the macroscale component of entropy at the expense of the mesoscale component [128]. Crack heal- ing decreases then disorder (and entropy) as observed at the macroscale, while fracture of the microcapsules in- creases disorder (and entropy) when observed at the mesoscale. Self healing occurs thus autonomically if the net entropy of the system is increasing and if the rate of healing is higher than the rate of degradation; the effec- tiveness of the healing mechanism can be influenced or perhaps measured using relating microstructure parame- ters to the entropy. It is important to stress that self-repair is not simply a material property, but rather a system property. There- fore, it is not realistic to develop universal self-repairing systems being applicable in all sorts of applications. Consequently, it is important to develop new concepts of self-repairing systems with additional values compared to the existing one, which are focused on a well-defined area/field of applications. However, the self-repair mechanisms used in most current systems and devices are not yet as developed as in the complex functional systems as existing in nature. Existing autonomic self-healing processes need time (rest periods) and energy. However, the end product is neither aesthetically nor functionally perfect. Defects on a nanoscale size are randomly distributed in any material, mechanical loads during the use cause the formation of cracks initiated by the nanoscaled defects, which cause, in time, degradation of the material up to a possible catastrophic failure. A self-healing mechanism already initiated at a nano- scale offer many advantages for a more effective pre- vention of further propagation and growth of mi- cro-cracks as has been shown in a recent modelling study [129]. There, the self-healing process of materials with embedded “glue”-carrying cells, in the regime of the onset of the initial fatigue has been studied by three-dimensional numerical simulations within the percolation- model approach. The onset of material fatigue is delayed in such a system by development of a plateaulike time dependence of the material quality. In this low-damage regime, the changes in the conduc- tance and thus in similar transport and response proper- ties of the material can be used as measures of the ma- terial quality degradation. A feature found for three dimensions being much more profound than in ear- lier-studied two-dimensional systems, is the competi- tion between the healing cells. Even for low initial densities of the healing cells, they interfere with each other and reduce each other’s effective healing effi- ciency. Short-range healing means that cells affect their neighbourhood approximately within a distance equal to their size. Thus, in order not to interfere literally, not to waste glue, other healing cells should not be healing this whole neighbourhood; thus they must be about two “shells of influence” away. The exclusion radius is thus at least three times the cell radius, in terms of the cen- ter-to-center separation, it is likely even larger, de- pending on the specific geometry. Any architecture for self-healing systems should sat- isfy essential properties like adaptability, dynamicity, awareness, autonomy, robustness and distribution. From this analysis and discussions of the currently active and explored principles of self-repair the following require- ments for the design of an ultimate self-healing struc- ture/material can be formulated: A reflection mechanism to detect internal or exter- nal conditions for which the system should respond to sensing function of damage A reasoning mechanism to determine which ac- tions should be taken in order to response to an in- put from the reflection mechanism―the feedback to repair mechanism, signal transport A configuration mechanism to perform necessary changes to repair or optimize the system as directed by reasoning mechanism and activation of the repair mechanism (repair-on-demand)―transport of en- ergy and/or material, repair with the ability to “heal/fill” damage (e.g. volume increase!) Repair has to be either attributive or functional, may be single repair (only one time) or repeating repair Detection of success and of the status of the structure, recovery of the initial status No reduction of the performance of the matrix ma- terial by the self-repair functionality; good adhesion and bonding and sufficient thermo-mechanical
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 894 properties of the repair material Sufficient high stability of the self-repair functional- ity during processing and storage Such systems have been already constructed and will be discussed at two examples: 5.1. Self-Repairing Strategies and Structures Used in Current Electronic Devices One method of self-healing is to design a multiply re- dundant system that can reconfigure itself when dam- aged. Re-configurable control systems require three separate functions: failure detection and isolation to de- termine which components are no longer useful; pa- rameter identification to provide a model of the damaged structure, and online control design that uses information from the other two to re-establish control of the modified structure. This approach has been applied for some time already in re-configurable circuit hardware. This is par- ticularly the case for DRAM. As a typical industry case, the original yield before a built-in self repair (BISR) using redundant elements for repair for a 256-Mbit com- modity DRAM in a 0.11-micron CMOS process is al- most 0, yet the yield of the same product after repair can increase to more than 60%, and even to 80%. Here, the BISR consists of three main blocks: built-in self test (BIST), built-in redundancy analysis (BIRA), and ad- dress reconfiguration (AR) [130]. Typically, a BIST cir- cuit consists of a controller, a test pattern generator (TPG), a data comparator, and interface logic. The con- troller executes the test algorithm and issues commands for the TPG. One of the algorithms used is testing is the Syndrome identification algorithm. This method identi- fies fail patterns during the test process to increase spare allocation efficiency. After analysis, the AR circuit re- pairs the memory; e.g. it replaces the faulty memory elements with the fault-free, spare ones. This typically involves address remapping or address decoder recon- figuration. When the memory size increases, the total benefit as a combination of early-market entry benefit, test benefit, development cost and cost for the redundant memory grows quickly, because the yield decreases ex- ponentially when the memory size increases, and thus the BISR design shows its effectiveness in enhancing the yield. Development costs become negligible when pro- duction volume is high, because they are constant for the product. Self-repair systems are currently well known and in use in several electronic structures to maintain Figure 27. Flow diagram typical for a self-repairing structure used in electronic devices. Reprinted from Engineering Applications of Artificial Intelligence, Self-repair of embedded systems, 17, E. A. Coyle, L. P. Maguire, T. M. McGinnity, 1-9, Copyright (2004), with permission from Elsevier.
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 895 their reliability for a long time. In fact, embedded sys- tems are increasingly entrusted with critical tasks and it becomes crucial that these systems exhibit a high level of reliability. The increasing complexity of such systems makes production of defect-free systems extremely dif- ficult. Therefore, self-repair methodologies were intro- duced employing a unified modelling language and ge- netic algorithms and increasing the flexibility and reli- ability of such systems by enabling the transfer of func- tionalities between hardware and software. A flow dia- gram of the processes in such a system is shown in Fig- ure 27. In contrast to the majority of the already covered sys- tems, this system is an example where the functionality is related to information flow and not to mechanical or aesthetic or other main functionalities. Hence, also the flow of information is used as the signal in the diagnos- tic process and as the mobile part of the system, able to perform the repair action. The diagnostic circle ad- dresses the functionality during operation of the target system and decides whether the current configuration is able to deal with the isolated fault and to update the sys- tem resource value on demand resulting in new parti- tions, compilation and upload of the new partitions onto the system information. Industrial leaders like Microsoft, Sun Microsystems and IBM are carrying out research on autonomic self-healing systems, grid computing, soft- ware agents and middleware computing are typically strategies and software systems and hardware architec- ture are being developed with self-healing properties. A summary of the developments in this area is given re- cently by Gosh (2007) [131]. 5.2. Self-Repairing Bolted Joints Bolted joint, as one of the most common mechanical components in all types of engineering structures, are critical to the function of the structure and their failure could have huge costs or endanger lives. Unfortunately, bolted joints are subject to a variety of common modes of failure. These include self-loosening, shaking apart, breaking because of corrosion, stress cracking or fa- tigue, slippage (which can change the way a structure absorbs load, leakage of corrosive substances in the joint), and separation leading to rapid fatigue. One of the most frequent modes of failure for bolted joints is self-loosening. To reduce this mode of failure a concept of a self-sensing and self-healing bolted joint has been developed, consisting of structural members joined together by bolt and nut combinations equipped with piezoceramic and shape memory alloy elements [132] (see Figure 28(a)). This concept combines an imped- ance-based health- monitoring technique (monitoring of bolt tension and connection damage) together with actuators to restore tension in the system. The actuators are included in the joint as shape memory alloy (SMA) washers. The most common SMA is nickel-titanium, often referred to NiTi or Nitinol, a material that has the ability to convert heat to mechanical energy through a phase transition. The actuation ability of smart materials should also provide force to a smart structure to counteract damage once it is detected, introducing the possibility of self- healing structures as demonstrated on this example. The impedance method detects and inspects whether the damage threshold value has been reached or not, and provides a signal to activate the SMA actuator if needed. When damage occurs, temporary adjustments of the bolt tension can be achieved actively and remotely in order to restore lost torque for continued operation (see Figure 28(b)). Thus, this is an example for the construction of a self-monitoring and self-healing system that could be added to existing structures, and provides both condition monitoring and self repair. (a) (b) Figure 28. a) Bolted Joint Configuration with SMA washer and PZT impedance sensor, b) Part of the impedance spectrum of a tight, loose and by SMA actuation fastened bolt connec- tion. Reprinted by permission from IOP Publishing Ltd: [Smart Mater. Struct.] (Practical issues of activating self-repairing bolted joints, D. M. Peairs et al, 13, 1414), copyright (2004).
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 896 6. TOWARDS A NEW GENERATION OF SELF-HEALING SYSTEMS In order to develop a new generation of self-healing de- vices-smart structures, the following working areas need particular effort: 1) Development/design of sensing elements to be in- corporated within structures/surfaces which are able to trigger the self-repair process (signal transport, activa- tion of the repair mechanism). This means that, contrary to most of the model systems, the sensor function has to be further developed and extended with an active learn- ing functionality, able to differentiate and to detect damage, to interpret the obtained information and to trigger/stimulate the repair action on demand. These sensoric elements should be ideally structural parts of the system and should not detoriate the general function- ality of the system. 2) Development of transport/repair mechanisms for different activation energies/materials and different cir- cumstances (speed, temperature, amount of recovery). This is especially needed to widen the area of applica- tions of self-healing systems to more materials and sys- tems. Up to now, only a limited number of solutions are existing (encapsulated glues etc.), however, new princi- ples have to be developed and employed to cover a broader range of performance demands. 3) Development of multiple repair processes applica- ble and sufficient for the purpose. This relates especially to the speed of the repair action, which has to be ad- justed to the needs and rest time periods available. An- other need is the development of the action-on-de- mand-only, strongly coupled with the development of sensor/trigger mechanism. If an action-on-demand-only can be realized, then it will be easier to ensure the capa- bility of multiple repair actions. Such an action could be triggered by a concentration of stress which initiates the repair action while activating an initiator. Materials that anticipate damage and increase their strength where damage probability is largest like the system developed by nature for the maintenance of our skeleton are virtu- ally damage free, if enough energy and time for the con- stant maintenance actions is supplied and given. Alterna- tively, continuously active materials like present in a living polymerization will realize a perfect restoration of the undamaged state if more reactive monomers are sup- plied after damage, e.g. via capsules [133]. 4) Finally, methods must be developed to test and characterise the structures/devices and to quantify the success of the self-repair action. Up to now, there is only a minor understanding of quantification of the success of self-healing, mostly by measurement of mechanical per- formance, however, since self-healing is not necessarily only connected to mechanical damage, some measure of the quality of the self-repair has to be developed. If these requirements are met, then it will be possible to create truly smart structures, which sense their inter- nal state and external environment and based on the in- formation gained respond in a manner that fulfils their functional requirements. The primary advantage of mov- ing towards smart structures technology is the potential cost benefit of condition-based maintenance strategies and the prospective life extension that may be achieved through in-situ health monitoring. 7. CONCLUDING REMARKS Implementation of self-healing is not intended to deal with poor or inadequate application design, development flaws, and problems with the quality of materials or op- erational errors of systems and devices. However, it should respond to damage caused by external deteriora- tion factors. Thus, self-healing should offer great oppor- tunities for increases in durability and reliability, reduced maintenance and overall costs. This includes reduced material resources, since the usual over-design of mate- rials is no longer required. Repair will be addressed at the very position of first appearance of damage, mini- mizing the need to have self-repairing functionality throughout the whole system. Autonomic self-repair should be intrinsically con- nected with a minimization of the free energy of the system after experiencing damage (e.g. fracture would create additional surfaces and hence enhance the overall energy level of the system). However, this is not as easy and autonomic as it may seem, damage may only lead to another local minimum of the overall free energy and this would be in some cases difficult to detect for a given system. It is for example extremely difficult to detect the energy changes connected with a change in pure ap- pearance of a coating without having scratches and even more difficult to react with a repair action on such changes, however the changes would account for a damage of the esthetical function of the coating. As for now, most of the introduced synthetic self-healing sys- tems have still substantial short-comes, such as the liq- uid based capsule system, which requires a large amount of capsules to fulfil the function thereby reducing the mechanics of the system in a way that it can only be treated as a model system for fundamental studies [91] or the difficulty in filling and sealing of the liquid based capillary systems which limits applicability [82-90]. Fully autonomous systems need to provide currently a level of mobility which makes them rather unattractive as constructive materials [70]. However, the latest de- velopments show ways for possible solutions such as the application of liquid filled capsules in coating systems or flexible laminates [134,135], here enabling a functional
H. Fischer / Natural Science 2 (2010) 873-901 Copyright © 2010 SciRes. OPEN ACCESS 897 repair of a system as corrosion protection which has not the same constraints as a structural material or the use of the same strategy while deploying conductive particles in liquids and as such repairing conductive pathways [136]. The design principles of a self-healing system are universal, however the synthetic system solutions de- veloped so far are mostly special for the very circum- stances of the material system and the application (con- ditions), no universal solution exists applicable for all material systems. At the most basic level, a self-repairing system re- quires redundant capacity and the ability to use it effec- tively. The system must be capable of modifying the configuration of the target system in order to affect a repair. New design principles and strategies will be ap- plied, and finally self-repairing potential will only be incorporated where it is needed or where damage of the material, system or device is going to start. Self-repair will be universal in terms of materials and will follow universal design principles and hence can be applied anywhere. The overall capabilities required for a self- repairing system extend the application functionality specified by the system designers. The additional ele- ments required include monitoring, test, diagnosis, and repair capabilities. The system monitor must be able to analyse high-level system performance of the system against predefined performance benchmarks, continu- ously verifying the correctness of the operation of the process and bi-directionally communicating with the target system. The testing process also must have bi- directional communication to activate specific test se- quences and receive results. This process should exploit any built-in self-test (BIST) ability, and the testing re- sults are forwarded to the diagnostic process. Automat- ing the fault diagnosis process inherently demands the application of intelligent techniques. Finally, the self- repair process must be able to affect a repair based on the reduction in resources available, following isolation of the faulty components. If the original level of per- formance cannot be restored, the monitoring system must be modified to reflect the changes in system char- acteristics. This feature demands an optimisation capa- bility. Providing these additional capabilities impose a significant burden on the system, there is a trade-off between the additional cost of the system to facilitate self-repair and the potential cost of failure. The purpose of this reflection is not to provide a re- view of the knowledge on self-healing systems; there- fore, it is by far not covering all work on this subject. The analysis of the systems as discussed in this work shows that the creation of self-healing systems is and is becoming reality. Although a number of synthetically designed self-healing systems are developed and still under development, they mostly fulfil only partially all requirements of an ideal self-healing system as produced by nature. The knowledge of the system complexity enables the design of a self-healing system for a given application and possible damage. The introduction of self-healing properties into materials systems is with this knowledge and an interdisciplinary approach of design combining all disciplines of science is a growing reality, which has been already demonstrated for a number of synthetic model systems and will have a great future in materials technology especially for systems used in maintenance critical applications such as areas with limited accessi- bility, high demands of reliability, a guaranteed long life or in areas where repairs cause a lot of hindrance/ an- noyance/costs. 8. AKNOWLEDGEMENTS The author acknowledges numerous stimulating discussions within the Delft Centre for Materials (DCMat) and the Innovative Research Pro- gram “Self-Healing Materials” of the Dutch Government and espe- cially within the group Fundamentals of Advanced Materials during the weekly stays as Visiting Scientist at the Faculty of Aerospace En- gineering at the TU Delft, Netherlands. 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