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Paladugu, S.R.M.;  Sreekanth, P.S.R.;  Sahu, S.K.;  Naresh, K.;  Karthick, S.A.;  Venkateshwaran, N.;  Ramoni, M.;  Mensah, R.A.;  Das, O.;  Shanmugam, R. Self-Healing Polymer, Metal, and Ceramic Matrix Composites. Encyclopedia. Available online: (accessed on 30 November 2023).
Paladugu SRM,  Sreekanth PSR,  Sahu SK,  Naresh K,  Karthick SA,  Venkateshwaran N, et al. Self-Healing Polymer, Metal, and Ceramic Matrix Composites. Encyclopedia. Available at: Accessed November 30, 2023.
Paladugu, Sri Ram Murthy, P. S. Rama Sreekanth, Santosh Kumar Sahu, K. Naresh, S. Arun Karthick, N. Venkateshwaran, Monsuru Ramoni, Rhoda Afriyie Mensah, Oisik Das, Ragavanantham Shanmugam. "Self-Healing Polymer, Metal, and Ceramic Matrix Composites" Encyclopedia, (accessed November 30, 2023).
Paladugu, S.R.M.,  Sreekanth, P.S.R.,  Sahu, S.K.,  Naresh, K.,  Karthick, S.A.,  Venkateshwaran, N.,  Ramoni, M.,  Mensah, R.A.,  Das, O., & Shanmugam, R.(2022, December 06). Self-Healing Polymer, Metal, and Ceramic Matrix Composites. In Encyclopedia.
Paladugu, Sri Ram Murthy, et al. "Self-Healing Polymer, Metal, and Ceramic Matrix Composites." Encyclopedia. Web. 06 December, 2022.
Self-Healing Polymer, Metal, and Ceramic Matrix Composites

Composites can be divided into three groups based on their matrix materials, namely polymer, metal and ceramic. Composite materials fail due to micro cracks. Repairing is complex and almost impossible if cracks appear on the surface and interior, which minimizes reliability and material life. In order to save the material from failure and prolong its lifetime without compromising mechanical properties, self-healing is one of the emerging and best techniques. 

microcapsules hollow fibers vascular network healing mechanisms

1. Introduction

Materials with self-healing capability have gained much attention recently. For example, scratches on a car can be patched or repaired on their own, restoring its original shiny appearance. This is somewhat similar to wound healing in mammals [1]. Structural materials deteriorate and degrade over time leading to micro-cracks that cause failure. Accordingly, to improve the reliability and lifetime of products, repair is necessary [2]. However, it is quite challenging to integrate the healing process of extreme conditions such as fractured bones into manufacturing products due to changing trends in the healing mechanisms of human bodies and other living beings [3].
Self-healing composites are capable of auto-repairing upon crack initiation and regaining their mechanical properties without disturbing the mode of application. Self-healing mechanisms can be divided into two types, extrinsic and intrinsic healing. In extrinsic healing, the healing agent is used as an additive to fill up the cracks in the matrix and in intrinsic healing, a reversible crosslinking bond (supramolecular chemistry) is used to bind the monomers and fill the cracks [4]. Furthermore, classification can also be made on autonomic healing or non-autonomic healing (i.e., with or without external stimuli). A few well-known methods for developing self-healing composites are the inclusion of microcapsules, hollow fibers, and a vascular network containing healing agents. Self-healing can also be achieved by thermal activation of reversible interactions or dissolved thermoplastic polymers [5].
The self-healing concept is an emerging technique in the engineering field and it can be applied to composite materials such as polymer matrix composites (PMCs), ceramic matrix composites (CMCs), metal matrix composites (MMCs), and cementitious composites. Apart from the specified areas, the self-healing concept can also be applied to coatings for corrosion protection for commercial applications [6][7]. Many potential applications of self-healing composites are implemented in resistant fabrics, resealing tires, long-life batteries, aerospace sectors, and automobile fields. In the aerospace sector, the damage due to impact load is severe [8]. However, self-healing materials can repair damage caused due to outside environment and increase the lifetime of the components. One key application of self-healing materials is to repair dynamic damage and maintain impact resistance [9].

2. Self-Healing of Metals and Metal Matrix Composites

2.1. Classification of Metallic Structures in Self-Healing

The self-healing procedures of revolutionary metallic materials are classified according to their product composition or autonomy (Figure 1). Additional actuation, such as applying heat or electricity, is essential for non-autonomous self-healing systems. Even though autonomous self-healing materials do not require outside actuation, autonomous metallic self-healing systems continue to be mostly theoretical currently, due to a lack of noticeable experimental results. Self-healing metal matrix composites (MMCs) are homogeneous macroscopic materials, formed from memory alloy (SMA) fibers and encapsulated healing chemicals commonly spread in a matrix. Irrespective of size, SMA wires are already placed in metal matrices (Al, Zn, Sn, or alloy that is Sn-Bi) as reinforcements to produce self-healing materials centered on SMA. Self-healing, depending on encapsulated recovery agents, is established by injecting capsules or pipes carrying a representation that is curing as solder [10][11][12][13]. Recovery through coatings, electro-heating, eutectic-based, and precipitation-based recovery are typical examples of self-healing [14][15][16][17]. Theoretical research focuses on nano-scale processes, including nano-SMA and ground boundary migration self-healing metals.
Figure 1. Methods of self-healing metals [18].

2.2. Mechanisms of Self-Healing Metal and MMCs

2.2.1. Precipitation-Dependent Healing

In precipitation-based recovery, micro-cracks/voids in the substance behave as nucleation areas for supersaturated or under-aged alloy precipitation. Solute atoms happen to be defects and voids in underaged alloys, in essence, “healing” them. This procedure shows the void as the outcome of being filled by migrant atoms in self-recovery and being examined. This healing, nonetheless, happens on a nanometer scale level comparable to the standard age-hardening process; however, it cannot fix heavy cracks. Precipitation occurs at microcracks that generate precipitates within the localized, highly stressed location, and recovery can be expedited by warming an alloy to an aging temperature that is particular. [19]. If the alloy cools, it becomes supersaturated meta-stable from high heat, and then returns to equilibrium, which happens during aging by precipitating supersaturated solutes over voids and cracks. An under-aged alloy such as Al-Cu-Ag-Mg increases its creep resistance by heat treating at high temperature but at a constraint rather than fully hardened, e.g., to T6 temper, dynamic precipitation of the following alloy even at 500 h creep at 300 MPa and 150 °C, even associated with dislocations and healing of the cracks, is obtained by further aging of heat treatment.
The curing of the break triggered additional heat that is aged. Precipitation heat treatment impacts the crack action in Al-Cu AA 2001 alloy in under-aged boundary situations, which has been investigated [20]. It indicates the microstructures of the under-aged alloy were crack healed after the aging treatment for 10 h. The work [21] studied the precipitation of boron nitride (BN), which leads to a self-healing mechanism in 304 stainless steel improvised with boron (B), cerium (Ce), and titanium (Ti). The alteration of B, Ce, and Ti of the alloy contributed towards the preferential BN accumulation in the locations associated with the creep cavity, and it is stable at high temperatures at creep cavity surfaces and leads to an increase in the creep resistance of 304 stainless steel. This procedure, as conducted over voids, holes, and other free surfaces, is heterogeneous to attain self-healing, which will behave as nucleation in odd cracks. Researchers examined how precipitation heals in two different areas. Precipitation recovery at high temperatures (575–750 °C) was mostly examined on stainless steel and Cr-Mo-V alloys, although it was mostly studied on Al alloys at low conditions (120–185 °C). Diffusion, which is the rate-constrained site that can manage the motion of atoms to the matrix and into gaps and fissures in the matrix, requires some time to accelerate. Precipitation-based recovery has thus far been limited to small-scale injury by studies. This can remove fatigue fracture start sites over extended periods, although restricted to early harm stages. Precipitation-based mending could have a small effect if a break widens.

2.2.2. Healing Based on Nano-SMA-Dispersoids

Nanosize shape memory alloy (nano-SMA) dispersoids were suggested for self-healing metallic materials. Period change of SMA nanoparticles, which belongs to the grouped community of nanoscale recovery processes, fills nano-voids. Few authors stated that the essential idea is currently in its very early phases of development. Additionally, the capability to self-heal has yet to be proved. The microstructure is first made up of a host matrix with embedded coherent SMA nanoparticles stabilized by the host matrix in its austenite phase which is a high-temperature zone [22][23][24][25][26]. Whenever damage is generated by dislocation localization and nanovoids are formed, activation of nanoparticles occurs, and the nanovoid strain is expected to change the phase transition of the SMA nanoparticle from austenite to martensite [27]. The change of phases is followed closely by a sharp change in the shape of the particle that produces regional stress areas on the host matrix and plays a part in the closing of cracks.
Theoretically, when small-size nano-dispersions fill voids, it can cause residual stresses and alter the fatigue characteristics of the material. The unit’s absence of bonding capabilities could be a performance impediment on the other side.

2.2.3. SMA-Based Healing

Self-healing materials with memory components aid in regenerating bulk geometry after having a fracture which is a feature not found in other self-healing modes. This is crucial regarding restoring a building’s previous functionality after significant damage. SMA reinforcements are utilized in selected steel matrices for self-healing in this technique. Shape pseudoelasticity and memory are two characteristics that distinguish SMAs. Whenever heated above its austenite transformation temperature, an SMA’s ability to deform into the martensitic state and then return to its original shape is known as pseudoelasticity [28]. The latter is connected with an SMA that can recover the strain which is highly applied upon unloading the material when it is in its austenite phase. In self-healing materials, heating at a high temperature helps to achieve substantial recovery by constraining shape recovery, which can lead to geometric reconstruction and crack closure. SMA has been enhanced to aid the healing process; nevertheless, the services and products remain essentially non-autonomous and need external actuation (typically heating).
The primary challenges encountered by self-healing SMA-reinforced materials, are (I) maintaining the bond between the SMA and matrix. (II) Synthesis affinity between SMA and the steel matrix; (III) The characteristics and recovery kinetics of SMA-reinforced matrix. (IV) SMA-metal matrix compatibility during synthesis; (V) An intensive knowledge of the dynamics and recovery kinetics of SMA-reinforced matrix; (VI) A clear understanding of the damaged area and how to speed the recovery process up. A self-healing material that is tin (Sn)-based was created using a strengthened Sn-21 Bi (wt. %) matrix alloy with 1% equiatomic NiTi SMA wires [29]. The composite, which contained a matrix that is complete in a tensile test, cooled to atmospheric temperature, and tested again, was fixed within an oven at 169 °C for 24 hours. The break, along with the restored specimens, was indeed found to be closed. It was unearthed that 95% of the original tensile strength was recoverable. The design was preserved by warming the SMA and softening the matrix solders. During heating, NiTi cables started to stress the matrix to recover to their original form (shorter lengths) The usage of other alloys as matrix materials for self-healing components has additionally been investigated. In experiments on healing, in a matrix that is magnesium-dependent partial recovery can happen at a given temperature. Qiao et al. [30] investigated the utilization of NiTi SMA wires within an Al-A380 matrix. Due to a lack of adhesion between the cable and the matrix, SMA cables alone were not able to repair the damaged faces. Wrapping SMA wire along the threaded stainless steel and casting Al-A380 around the rod/wire addressed the challenge. This rod acted as a technical anchor, allowing the SMA to pull, although the whole cable had disintegrated. It was discovered that the strengthened component was approximately twice as strong and ductile due to the unreinforced sample. Since the re-bonding was inadequate, there was no significant power, although a significant decrease in fracture width and residual compressive stresses was observed. Because SMA is now a part of self-healing, limited rehabilitation may now be used to produce recurring compressive stress fracture repair. This residual load by post-tensioned tangible systems enables the structure to withstand externally induced stress without bonding. Continuous initiatives are fond of describing this possibility in terms of how healing systems may be constructed to withstand axial or external bending stresses. Since applied stress rises, adhesive bond energy grows; this capacity is thought to aid bonding in self-healing.

2.2.4. Encapsulated Healing

In this section, the healing performance of capsule-based self-healing materials is discussed. Table 1 shows the healing performance of capsule-based self-healing materials. Microcapsules containing dicyclopentadiene (DCDP), a monomer curing representative, were embedded inside a polymeric epoxy matrix, including a catalyst to achieve the self-healing of autonomous polymers. Self-healing happens when capsules that discharge the agent (a monomer) are propagated and broken by a break in polymeric materials. Encapsulated agents treatments, such as polymer healing agents, have been utilized to create self-healing MMCs. Ferguson et al. [31] proposed the growth of the latest MMCs being self-healing encapsulated solders in 2008. Materials with low melting temperatures were encased in ceramic shells to identify the breach and then scattered within a host matrix with a greater melting temperature [32][33][34]. After heating, the solders had low temperatures and flooded into the fracture, charging the space by capillary action and starting bonding at particular conditions. The energy data recovery with this curing procedure depends on this host steel structure; therefore, the properties of alloys having a low melting temperature exhibited an energy restoration of 60% associated with the initial pre-damaged energy [35][36][37][38].
Table 1. Healing performance of capsule-based self-healing materials [39].
Mechanism Healing Percentage (%) Time for Healing (hrs) Conditions for Healing Matrix Reference
DCPD + Grubbs 75–100 10–48 Room temperature Epoxy [40]
DCPD + Grubbs 30 24 Room temperature Epoxy vinyl ester [40]
DCPD + Grubbs 70–100 48 Room temperature Epoxy + CFRC [40]
DCPD + WCl6 20–64 24 25–50 °C Epoxy [41]
ENB + Grubbs 45–80 48 Room temperature- 80 °C Epoxy [42]
ENB/DCPD+ Grubbs 85 48 Room Temperature Epoxy [42]
ENB + Hoveyda Grubbs 95 2 170 °C Epoxy [42]
HOPDMS and PDES 20–24 24 50 °C Epoxy vinyl ester [43]
HOPDMS and PDES 100 48 150 °C Epoxy +FRC [43]
Epoxy and Solvent 85–100 24 Room Temperature Epoxy [44]
Epoxy and Solvent + Scandium triflate More than 80 48 80 °C Epoxy [30]
Epoxy + CuBr (2) (2-Melm)4 111 1.5 130 °C-180 °C Epoxy [45]
Epoxy + Mercaptan 104 24 20 °C Epoxy [45]
Epoxy + MBM tetrathol 120 5 days 25 °C Epoxy [46]
Epoxy + antimony pentafluoride 70 20 sec Room temperature at 0.2 MPa Epoxy [46]

2.2.5. Coating-Based Healing

The authors created the facet of the titanium alloy with a thickness of 2.03 mm, a 60 percent indium–40 percent tin (wt. percent) self-healing coating with a melting temperature of 124 °C and a thickness range of 0.005–0.0015 mm. If a surface break appears, these devices may be heated through the In–Sn alloy’s melting point. As soon as the specimen is heated, the break in the titanium alloy is covered by molten area alloys [47][48][49][50]. Crack healing evaluation revealed that after the procedure, which is a self-healing process, crack development is avoided by employing a low crack-tip driving force. An increased crack-tip driving force can result in a 50% reduction in the break development rate. The self-healing coating could be activated repeatedly, indicating the chance of multicycle heating in inert conditions.

2.2.6. Electro Healing

Steel ions are electrodeposited onto a fracture in a bath with electrolytic-regulated electric currents in pure nickel sheets, resulting in break recovery. The authors examined electro-healing. The cracks with sizes up to 100 µm within the micrometer range had been effectively healed utilizing the procedure of electro-healing. This action has regained almost 96 percent of tensile power. While this option would be effective, there could be a limitation to the need to place a framework combined with a small scale of heating.

2.2.7. Eutectic-Based Recovery

Numerous researchers [51][52][53][54] examined eutectic-based healing using eutectic liquid formed in its solid phase and acting as a healing region, while the solid dendrites are composed of structural integrity. The best path to accomplish this is to use a matrix that is distant from eutectic composition to form eutectic dendrites at higher temperatures. When the melt is cooled, dendrites of this main period are created because of their high melting temperature. These dendrites deform the structure of the remaining inter-dendritic fluid, repelling the dissolved substances, so the composition of the inter-dendritic fluid changes. To achieve this for self-healing, the temperature has to be increased until the interdendritic eutectic melts and flows into the specimen through the mechanism of cracks and then closes the crack, while the hard dendrites keep the structural coherence of the system. The fluid is a eutectic movement involving the dendrites and enters any holes or gaps within the unit; the eutectic liquid solidifies in the cracks and heals the specimen, as shown in Figure 2.
Figure 2. Liquid-aided healing of MMCs reinforced with SMA [55].

2.3. Applications and Future Scope

The attractive advantages of the usage of self-recovery in metal substances include low renovation costs, lengthy carrier life, and avoidance of catastrophic remarks. However, self-recovery in metal substances has not been extensively utilized in real-international applications, particularly for load-bearing applications. MMCs with self-recovery traits are being evaluated properly now. Self-recovery metals and substances are not blanketed in any purchaser products. Self-recovery polymers crafted from MMCs, which include self-recovery slicing pads, are currently commercially viable. Nonetheless, self-recovery metals and self-recovery MMCs have several uses. In the renewable strength and biomedical sectors, self-recovery metallic substances with sturdy mechanical properties can be created for wing parts, structural components, spinning components, blades of turbines, and steel implants.


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