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Here, a polysaccharide derivative acryloyl chitosan (AcCS) is exploited as macro-crosslinker to synthesize a novel ionogel poly (acrylic acid-co-1-Vinyl-3-butyl imidazolium chloride) (AA-IL/AcCS) via a one-pot method. AcCS provides abundant physical and chemical crosslinking sites contributing to the high mechanical stretchability (elongation at break 600 %) and strength (tensile strength 137 kPa) of AA-IL/AcCS. The high-density of dynamic bonds (hydrogen bonds and electrostatic interactions) in the network of ionogels enables self-healing and self-adhesive features of AA-IL/AcCS. Meanwhile, AA-IL/AcCS exhibits high ionic conductivity (0.1 mS/cm) at room temperature and excellent antifreeze ability (-58 °C). The AA-IL/AcCS-based sensor shows diverse sensory capabilities towards temperature and humidity, moreover, it could precisely detect human motions and handwritings signals. Furthermore, AA-IL/AcCS exhibits excellent bactericidal properties against both gram-positive and gram-negative bacteria. This work opens the possibility of polysaccharides as a macro-crosslinkers for preparing ionogel-based sensors for wearable electronics.

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In situ forming hydrogels are promising for biomedical applications, especially in drug delivery. The precursor solution can be injected at the target site, where it undergoes a sol-gel transition to afford a hydrogel. In this sense, the most significant characteristic of these hydrogels is fast gelation behavior after injection. This study describes an all-polysaccharide, rapidly in situ-forming hydrogel composed of carboxymethyl chitosan (CMCHT) and hydroxyethyl cellulose functionalized with aldehyde groups (HEC-Ald). The HEC-Ald was synthesized through acetal functionalization, followed by acid deprotection. This innovative approach avoids cleavage of pyran rings, as is inherent in the periodate oxidation approach, which is the most common method currently employed for adding aldehyde groups to polysaccharides. The resulting hydrogel exhibited fast stress relaxation, self-healing properties, and pH sensitivity, which allowed it to control the release of an encapsulated model drug in response to the medium pH. Based on the collected data, the HEC-Ald/CMCHT hydrogels show promise as pH-sensitive drug carriers.

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Self-healing materials inspire the next generation of multifunctional wearables and Internet of Things appliances. They expand the realm of thin film fabrication, enabling seamless conformational coverage irrespective of the shape complexity and surface geometry for electronic skins, smart textiles, soft robotics, and energy storage devices. Within this context, the layer-by-layer (LbL) technique is versatile for homogeneously dispersing materials onto various matrices. Moreover, it provides molecular level thickness control and coverage on practically any surface, with poly(ethylenimine) (PEI) and poly(acrylic acid) (PAA) being the most used materials primarily employed in self-healing LbL structures operating at room temperature. However, achieving thin film composites displaying controlled conductivity and healing ability is still challenging under ambient conditions. Here, PEI and PAA are mixed with conductive fillers (gold nanorods, poly(3,4-ethylene dioxythiophene): polystyrenesulfonate (PEDOT:PSS), reduced graphene oxides, and multiwalled carbon nanotubes) in distinct LbL film architectures. Electrical (AC and DC), optical (Raman spectroscopy), and mechanical (nanoindentation) measurements are used for characterizing composite structures and properties. A delicate balance among electrical, mechanical, and structural characteristics must be accomplished for a controlled design of conductive self-healing composites. As a proof-of-concept, four LbL composites were chosen as sensing units in the first reported self-healing e-tongue. The sensor can easily distinguish basic tastes at low molar concentrations and differentiate trace levels of glucose in artificial sweat. The formed nanostructures enable smart coverages that have unique features for solving current technological challenges.

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Ionenes are poly(ionic liquids) (PILs) comprising a polymer backbone with ionic groups along the structure. Ionenes as solid-solid phase change materials are a recent research field, and some studies have demonstrated their potential in thermal dissipation into electronic devices. Eight ionenes obtained through Menshutkin reactions were synthesized and characterized. The analysis of the thermal tests allowed understanding of how the thermal properties of the polymers depend on the aliphatic nature of the dihalogenated monomer and the carbon chain length. The TGA studies concluded that the ionenes were thermally stable with T10% above 420 °C. The DSC tests showed that the prepared ionenes presented solid-solid transitions, and no melting temperature was appreciated, which rules out the possibility of solid-liquid transitions. All ionenes were soluble in common polar aprotic solvents. The hydrophilicity of the synthesized ionenes was studied by the contact angle method, and their total surface energy was calculated. Self-healing behavior was preliminarily explored using a selected sample. Our studies show that the prepared ionenes exhibit properties that make them potential candidates for applications as solid-solid phase change materials.

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Supramolecular structures are of great interest due to their applicability in various scientific and industrial fields. The sensible definition of supramolecular molecules is being set by investigators who, because of the different sensitivities of their methods and observational timescales, may have different views on as to what constitutes these supramolecular structures. Furthermore, diverse polymers have been found to offer unique avenues for multifunctional systems with properties in industrial medicine applications. Aspects of this review provide different conceptual strategies to address the molecular design, properties, and potential applications of self-assembly materials and the use of metal coordination as a feasible and useful strategy for constructing complex supramolecular structures. This review also addresses systems that are based on hydrogel chemistry and the enormous opportunities to design specific structures for applications that demand enormous specificity. According to the current research status on supramolecular hydrogels, the central ideas in the present review are classic topics that, however, are and will be of great importance, especially the hydrogels that have substantial potential applications in drug delivery systems, ophthalmic products, adhesive hydrogels, and electrically conductive hydrogels. The potential interest shown in the technology involving supramolecular hydrogels is clear from what we can retrieve from the Web of Science.

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This study aimed to determine an optimal dosage of sunflower oil (i.e., Virgin Cooking Oil, VCO) as a rejuvenator for asphalt self-healing purposes, evaluating its effect on the chemical (carbonyl, and sulfoxide functional groups), physical (penetration, softening point, and viscosity), and rheological (dynamic shear modulus, and phase angle) properties of long-term aged (LTA) bitumen. Five concentrations of sunflower oil (VCO) were used: 1%, 2%, 3%, 4%, and 5% vol. of LTA bitumen. VCO was encapsulated in alginate biopolymer under vibrating jet technology using three biopolymer:oil (B:O) mass ratios: 1:1, 1:5, and 1:9. The physical, thermal, and mechanical properties of the capsules were studied, as well as their effect on the physical properties of dense asphalt mixtures. The main results showed that an optimal VCO content of 4% vol. restored the chemical, physical, and rheological properties of LTA bitumen to a short-term ageing (STA) level. VCO capsules with B:O ratios of 1:5 presented good thermal and mechanical stability, with high encapsulation efficiency. Depending on the B:O ratio, the VCO capsule dosage to rejuvenate LTA bitumen and asphalt mixtures varied between 5.03-15.3% wt. and 0.24-0.74% wt., respectively. Finally, the capsule morphology significantly influenced the bulk density of the asphalt mixtures.

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This study evaluated the effect of two encapsulation methods (i.e., dropping funnel and syringe pump), two concentrations of the alginate-based encapsulating material (2%, and 3%), and three oils as bitumen rejuvenators (virgin sunflower oil, waste cooking oil, and virgin engine oil) on the morphological, physical, chemical, thermal, and mechanical properties of encapsulated rejuvenators for asphalt self-healing purposes. A general factorial design 2 × 2 × 3 was proposed to design 12 different Ca-alginate capsules. Significant differences on the morphological, physical, and mechanical properties of the capsules were analysed by three-way ANOVA and Tukey HSD Post Hoc analyses. The effect of the type of oil on the self-healing capacity of cracked bitumen samples was also evaluated. The main results showed that the design parameters and their interactions significantly affected the morphological, physical, and mechanical properties of the capsules. Capsules synthesised via syringe pump method, with virgin cooking oil and 2% alginate was the most appropriate for asphalt self-healing purposes since its uniform morphology, encapsulation efficiency up to 80%, thermal degradation below 5% wt., and compressive strength above the reference asphalt compaction load of 10 N. Finally, the healing tests showed that virgin cooking oil can be potentially used as a rejuvenator to promote asphalt crack-healing.

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OBJECTIVES: To evaluate the incorporation of repairing capsules containing different monomers and polymerization modulators on the self-healing efficiency of an experimental photopolymerizable resin-based composite. METHODS: Self-healing capsules containing different monomers and polymerization modulators were prepared by emulsion polymerization: TCDHEPT (TEGDMA and DHEPT), BTCDHEPT (Bis-GMA, TEGDMA, and DHEPT), and BTCBPO (Bis-GMA, TEGDMA, and BPO). The capsules were analyzed through Fourier transform infrared spectroscopy and scanning electron microscopy. The capsules were added into experimental photopolymerizable resin composites establishing the following groups: ER (Control without capsules), ER+BPO, ER+BPO+TCDHEPT, and ER+BTCBPO+BTCDHEPT. Filtek Z350 resin composite (3 M ESPE) was used as a commercial reference. The materials were tested for degree of conversion (DC), flexural strength (σf), elastic modulus (Ef), fracture toughness (virgin KIC), self-healing efficiency (healed KIC), and roughness. For statistical analysis, the significance value was established at an a = 0.05 level. RESULTS: When compared to the control material, the incorporation of repairing capsules did not affect DC, σf, and Ef. Fracture toughness was statistically similar between the experimental groups (p ≤ 0.05). Healed KIC was statistically different between the groups ER+TCDHEP and ER+BTCBPO+BTCDHEPT; the self-healing efficiency was higher for ER+TCDHEPT. Surface roughness was statistically similar among all groups. CONCLUSIONS: The use of self-healing capsules promoted repair of the material. Studies with material aging after the self-healing process are necessary to better demonstrate the effectiveness of this system. CLINICAL SIGNIFICANCE: The self-healing system seemed to be a promising technology to be used in self-repaired restorative materials, which may prevent restoration fractures.

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Asphalt pavements and bituminous composites are majorly damaged by bitumen aging and fatigue cracking by traffic load. To add, maintenance and reparation of asphalt pavements is expensive and also releases significant amounts of greenhouse gases. These issues can be mitigated by promoting asphalt self-healing mechanisms with encapsulated rejuvenators. The ability of the required microcapsules to be resilient against high temperatures, oxidation, and mechanical stress is essential to promote such self-healing behavior without compromising the field performance of the asphalt pavement. This work proposes, for the first time, the use of extremely resistant biobased spores for the encapsulation of recycled oil-based rejuvenators to produce more resilient self-healing pavements. Spore encapsulants were obtained from natural spores (Lycopodium clavatum) by applying different chemical treatments, which enabled the selection of the best morphologically intact and clean spore encapsulant. The physical, morphological, and physicochemical changes were examined using fluorescence images, ATR-FTIR, SEM, size distribution, XRD, TGA and DSC analyses. Sunflower oil was used as the encapsulated rejuvenator with an optimal sol colloidal mixture for sporopollenin-oil of 1:5 (gram-to-gram). Vacuum, passive, and centrifugal encapsulation techniques were tested for loading the rejuvenator inside the clean spores and for selecting the best encapsulation technology. The encapsulation efficiency and the profiles of the accelerated release of the rejuvenator from the loaded spores over time were studied, and these processes were visualized with optical and inverted fluorescence microscopy. Vacuum encapsulation was identified as the best loading technique with an encapsulation efficiency of 93.02 ± 3.71%. The rejuvenator was successfully encapsulated into the clean spores, as observed by optical and SEM morphologies. In agreement with the TGA and DSC, the microcapsules were stable up to 204 °C. Finally, a self-healing test was conducted through fluorescence tests to demonstrate how these biobased spore microcapsules completely heal a crack into an aged bitumen sample in 50 min.

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Microwave heating of asphalt pavement is a promising technique to reduce the maintenance and increase the service life of materials through self-healing of cracks. Previous studies have shown that microwave heating technology at high temperatures could damage the bitumen of asphalt mixture, which is an unwanted effect of the crack-healing technique. In this study, the effects of microwave heating and long-term aging on the rheological and chemical properties of recovered bitumen were quantified using a frequency sweep test and Fourier Transform Infrared Spectrometry analysis, respectively. The main results indicate that microwave heating has no significant effect on the aging performance of G* and δ for aged asphalt mixtures. However, for newer bitumens, the rheological properties G* and δ show minor changes after microwave heating was applied. Overall, this study confirms that microwave heating is a potential alternative for maintenance of asphalt pavements, without severely affecting the rheological and chemical properties of bitumen.

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Microencapsulation of curing agents is a major strategy for the development of self-healing polymers. Isocyanates are among the most promising compounds for the development of one-part, catalyst free, self-healing materials, but their microencapsulation is challenging due to their high reactivity. To keep the healing agent intact in the liquid state and containing free-NCO groups, the monitoring of several synthesis parameters is essential. This review aims to summarise the outcomes in the microencapsulation of isocyanates, emphasising the efforts reported in the literature to modulate the microcapsule properties. In this regard, the main synthesis procedures are presented, followed by the most relevant characterisation methods used to assess microcapsule properties. The correlation between these properties and synthesis parameters is also discussed, and finally the main potential and challenges for industrial applications are highlighted.

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Nowadays, the self-healing approach in materials science mainly relies on functionalized polymers used as matrices in nanocomposites. Through different physicochemical pathways and stimuli, these materials can undergo self-repairing mechanisms that represent a great advantage to prolonging materials service-life, thus avoiding early disposal. Particularly, the use of the Joule effect as an external stimulus for self-healing in conductive nanocomposites is under-reported in the literature. However, it is of particular importance because it incorporates nanofillers with tunable features thus producing multifunctional materials. The aim of this review is the comprehensive analysis of conductive polymer nanocomposites presenting reversible dynamic bonds and their energetical activation to perform self-healing through the Joule effect.

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The use of self-healing asphalt is a good option to extend the lifetime of roads and to improve the sustainability of pavement management systems. A bibliometric analysis based on the Scopus database was carried out to review the global research related to self-healing asphalt from 2003 to 2018 and to identify relevant quantitative characteristics from the research in this period. The results from this analysis revealed that the number of accumulated publications followed an exponential growth, which confirmed the relevance that this research topic has gained during the last years. The study revealed that China was the most productive country, followed by the Netherlands, where the most prolific institution is located: Delft University of Technology. Some important research features of the two main approaches most frequently used to develop asphalt mixtures with enhanced self-healing abilities (external heating and encapsulated rejuvenating agents) are compiled in this work.

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The use of microorganisms capable of mediating the bioprecipitation process can be an important application in the self-healing processes of cement specimens. Thus, the present study identified and evaluated five Bacillus strains for potential application in the protocol of self-healing via bioprecipitation. Cell growth, enzyme production, and kinetic parameters conditions were evaluated during the fermentation process. Based on the analysis of 16S rDNA in conjunction with biochemical testing, results demonstrate that the strains are either Bacillus cereus or Bacillus thuringiensis. Strategically it was found that the addition of glycerol to fermentative medium was essential to increase the bacterial concentration (≈ 4.2 × 107 cells mL-1) and production of the enzyme urease (≈ 3.623,2 U.mL-1). The addition of this medium after 40 days of fermentation promoted the self-healing of cracks and increased compressive strength in ≈ 14.2% of the cementitious specimens; therefore, increasing the sustainability and engineering properties of cement-based materials.

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Reinforced concrete structures are prone to cracking. The development of cementitious matrices with the capacity for self-healing soon after these cracks appear represents savings with inspections and repairs of the structures. Self-healing can be stimulated with the use of crystalline admixtures. Such materials easily react with water and increase the density of C-S-H (hydrated-calcium-silicate), forming insoluble deposits blocking existing pores and cracks. In this research, self-healing in concrete cracks was evaluated using three different crystalline admixtures, submitted to two and six wetting-drying cycles. The efficiency of self-healing was evaluated by optical microscopy and using the chloride diffusion test, which allowed calculating the predicted useful life of the concretes. The results highlight two important findings: (i) in optical microscopy, crystalline admixtures were not efficient in promoting self-healing on the surface of cracks in any of the studied concretes; (ii) the passage of chlorides by diffusion was lower for concretes with crystalline admixtures compared to the reference, showing better internal healing of these materials and, consequently, greater prediction of the concrete's useful life.

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Asphalt self-healing by encapsulated rejuvenating agents is considered a revolutionary technology for the autonomic crack-healing of aged asphalt pavements. This paper aims to explore the use of Bio-Oil (BO) obtained from liquefied agricultural biomass waste as a bio-based encapsulated rejuvenating agent for self-healing of bituminous materials. Novel BO capsules were synthesized using two simple dripping methods through dropping funnel and syringe pump devices, where the BO agent was microencapsulated by external ionic gelation in a biopolymer matrix of sodium alginate. Size, surface aspect, and elemental composition of the BO capsules were characterized by optical and scanning electron microscopy and energy-dispersive X-ray spectroscopy. Thermal stability and chemical properties of BO capsules and their components were assessed through thermogravimetric analysis (TGA-DTG) and Fourier-Transform Infrared spectroscopy (FTIR-ATR). The mechanical behavior of the capsules was evaluated by compressive and low-load micro-indentation tests. The self-healing efficiency over time of BO as a rejuvenating agent in cracked bitumen samples was quantified by fluorescence microscopy. Main results showed that the BO capsules presented an adequate morphology for the asphalt self-healing application, with good thermal stability and physical-chemical properties. It was also proven that the BO can diffuse in the bitumen reducing the viscosity and consequently self-healing the open microcracks.

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Resins of polyurethane were prepared from vegetable oils (crambe and castor) and modified by adding green corrosion inhibitor (condensed tannin). The oils were characterized by gas chromatography with flame-ionization detection (GC-FID), attenuated total reflectance Fourier transform infrared spectroscopy (FTIR-ATR) and thermogravimetric analysis (TGA). The reaction was monitored by characterizing the intermediate products (polyester and prepolymer). The polyester was characterized by solubility in methanol, acidity index, hydroxyl groups and FTIR-ATR, and the prepolymer was characterized by solid content, solvent content, isocyanate (NCO) groups and FTIR-ATR. The formation of PU resins was confirmed by FTIR-ATR and TGA, and the presence of tannin particles incorporated in the coating can be observed by optical microscopy (OM). The absence of the band attributed to NCO in FTIR-ATR spectra of the resins confirmed the complete reaction between polyester and prepolymer. The OM observation and a video demonstrate that Polyurethane (PU)-modified with condensed tannin resin presents self-healing effect, probably through the formation of new hydrogen bonds when in contact with deionized water. Therefore, these results open possibilities for new synthetic routes aiming at improving the very important self-healing property for protecting metals and their alloys against corrosion, extending significantly the metallic materials lifetime as previously demonstrated by our group.

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In this work, structural and active corrosion inhibition effects induced by lithium ion addition in organic-inorganic coatings based on poly(methyl methacrylate) (PMMA)-silica sol-gel coatings have been investigated. The addition of increasing amounts of lithium carbonate (0, 500, 1000, and 2000 ppm), yielded homogeneous hybrid coatings with increased connectivity of nanometric silica cross-link nodes, covalently linked to the PMMA matrix, and improved adhesion to the aluminum substrate (AA7075). Electrochemical impedance spectroscopy (EIS), performed in 3.5% NaCl aqueous solution, showed that the improved structural properties of coatings with higher lithium loadings result in an increased corrosion resistance, with an impedance modulus up to 50 GΩ cm2, and revealed that the lithium induced self-healing ability significantly improves their durability. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS) suggest that the regeneration process occurs by means of lithium ions leaching from the adjacent coating toward the corrosion spot, which is restored by a protective layer of precipitated Li rich aluminum hydroxide species. An analogue mechanism has been proposed for artificially scratched coatings presenting an increase of the impedance modulus after salt spray test compared to the lithium free coating. These results evidence the active role of lithium ions in improving the passive barrier of the PMMA-silica coating and in providing through the self-restoring ability a significantly extended service life of AA7075 alloy exposed to saline environment.

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Poly(urea-formaldehyde) (PUF) microcapsules filled with dicyclopentadiene (DCPD) were prepared by in situ polymerisation and the effect of synthesis parameters, such as pH of the solution and agitation rate, on microcapsules size and shell thickness was evaluated. Scanning electron microscopy (SEM) and Fourier transform infra-red spectroscopy (FTIR) were performed. Adjusted pH conditions (pH = 3.5) and agitation rate (1350 RPM) were found using a design of experiments (DOE). SEM results indicated that microcapsule size was directly affected by agitation rate, whereas shell thickness was mostly affected by pH. After obtaining adjusted synthesis conditions, microcapsules presenting mean size of 60 µm and mean shell thickness of 4 µm were embedded in an epoxy matrix for evaluating the self-healing effect. FTIR and SEM analyses in damaged samples suggested that a healing agent was delivered to the crack location.

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Introdução: A esclerose múltipla, doença neurológica crônica, de evolução contínua e diferenciada, demanda autoconhecimento do corpo, para melhor percepção das capacidades preservadas, das perdas gradativas e da repercussão na realização das atividades e na participação social. Objetivo: Analisar a experiência grupal de aplicação das técnicas corporais baseadas no método self-healing, para a promoção da saúde e reabilitação de pessoas com esclerose múltipla, desenvolvida pela terapia ocupacional. Método: Pesquisa qualitativa do tipo documental referente aos registros escritos e áudios transcritos das sessões grupais. Para análise dos dados foi utilizado o método do Discurso do Sujeito Coletivo. Resultados: Participaram do grupo terapêutico 10 adultos com esclerose múltipla, com idades e tempos de doença variados. Foram identificados cinco discursos relacionados às representações e experiências decorrentes da doença e dos efeitos do aprendizado das técnicas corporais do método self-healing. Como benefícios destacam-se maior percepção corporal, diminuição dos sintomas, melhora da capacidade funcional e reconhecimento da necessidade da prática corporal na rotina. Conclusão: O uso terapêutico do método self-healing demonstrou sua plicabilidade para a promoção da saúde e reabilitação, em conformidade com as políticas da saúde. Dada a pouca literatura existente sobre os benefícios do uso do método self-healing indica-se o desenvolvimento de novos estudos.

Introduction: Multiple sclerosis is a neurological chronic disease with continuous and differentiated evolution, it demands body self-knowledge for better understanding of preserved capacities, gradual losses and repercussion in the performance of activities and social participation. Objective: To analyze the group experience of the application of physical techniques based on self-healing method for health promotion and rehabilitation of people with multiple sclerosis, developed by Occupational Therapy. Method: Documental qualitative research referring to written records and audio transcripts of group sessions. Data analysis used the Collective Subject Discourse method. Results: Ten adults with multiple sclerosis, with varying ages and disease times, participated in the therapeutic group. Five participants reported representations and experiences due to the disease and the effect of learning the physical techniques of self-sealing. The benefits include a greater body awareness, decreased symptoms, improved functional capacity and recognition of the need of body practice routine. Conclusion: The therapeutic use of self-healing method demonstrated its applicability to promote the health benefits, rehabilitation, according to health policies. Due to limited literature on the benefits of using the self-healing method indicates the development of new studies.