Self-healing Epoxy Research Articles

Bio-Based Self-Healing Epoxy Vitrimers with Dynamic Imine and Disulfide Bonds Derived from Vanillin, Cystamine, and Dimer Diamine.

The condensation reactions of 4,4'-(ethane-1,2-diylbis (oxy)) bis(3-methoxybenzaldehyde) (VV) with cystamine, 1,6-hexamenthylene diamine, and a dimer diamine (PriamineTM 1075) produced three types of vanillin-derived imine-and disulfide-containing diamines (VC, VH, and VD, respectively). Thermal curing reactions of polyglycerol polyglycidyl ether with VD and mixtures of VC/VD and VH/VD produced bio-based epoxy vitrimers (BEV-VD, BEV-VC/VD, and BEV-VH/VD, respectively). The degree of swelling and gel fraction tests revealed the formation of a network structure, and the crosslinking density increased with a decreasing VD fraction. The glass transition temperature, tensile strength, and tensile modulus of the cured films increased as the VD fraction decreased. In contrast, the thermal degradation temperature of the cured films increased as the VD fraction increased. All the cured films were healed by hot pressing at 120 °C for 2 h under 1 MPa at least three times. The healing efficiencies, based on tensile strength after the first healing treatment, were 75-78%, which gradually decreased as the healing cycle was repeated. When imine-and disulfide-containing BEV-VC/VD and imine-containing BEV-VH/VD with the same VC/VD and VH/VD ratios were used, the former exhibited a slightly higher healing efficiency.

Mussel-inspired polydopamine (PDA)-grafted 2D-Ti3C2 MXene nanosheets tailored ZnAl-layered double hydroxides (LDH); Toward designing a smart self-healing epoxy composite coating

The constant challenge of corrosion significantly compromises the durability and functionality of metal substrates, propelling the demand for advanced protective solutions. This study introduces a novel smart epoxy coating system modified with a three-component nanocomposite integrating polydopamine (PDA)-modified Ti3C2 MXene with ZnAl-layered double hydroxides (LDH), intercalated with phosphate (P) and glutamate (Gl) ions as corrosion inhibitors. The innovative approach leverages the synergistic impacts of barrier protection, ion exchangeability, and self-healing capabilities to offer superior anti-corrosion performance. In the solution phase, the EIS results revealed a notable increase in resistance values, with MPLG samples exhibiting a 2.45-fold and MPLP samples a 2.17-fold enhancement compared to the blank specimen after 96 h of immersion. Furthermore, the data obtained from EIS demonstrated a significant enhancement in the barrier effects of the epoxy coating upon the addition of MPLG and MPLP. This enhancement was evidenced by a significant increase in the impedance values, which were observed to be 103-fold higher following a prolonged immersion period of 140 days. The self-healing properties, confirmed through EIS, FE-SEM, and EDX/Mapping analyses, indicated the formation of a stable corrosion-protective layer over the damaged areas, thus providing active protection. Adhesion assessments further underscored the coatings' durability, with MPLG and MPLP samples demonstrating minimal delamination. Collectively, these findings emphasize the potential of the proposed PDA-modified MXene@ZnAl-LDH nanocomposite as a multifaceted solution to corrosion challenges, promising significant advancements in the longevity and reliability of coated metal surfaces.

Design of self-healing and anticorrosion epoxy coating with active multiple hydrogen bonds based on grafted polyetheramine

The healing of epoxy coatings in damaged areas significantly influences their service life and protection quality. Intrinsic self-healing coatings, which enable multiple healing cycles without the need for additional functional carriers, have emerged as a promising coating technology. Nevertheless, the cross-linked structure of thermoset epoxy coating system restricts the large-scale migration of molecular chains, posing a significant challenge to achieve intrinsic healing of resin without compromising its mechanical properties. In this study, we report a design scheme for epoxy coating with intrinsic self-healing properties based on active multiple hydrogen bonds. Grafting aminobenzothiazole at the end of polyetheramine D230 chain, the grafted polyetheramine (GD230) was synthesized and served as the auxiliary curing agent, whose accurate molecular structure has been confirmed by different characterizations. The self-healing coating with reversible dynamics network based on hydrogen bonds was prepared by crosslinking through epoxy resin and mixed curing agent of polyetheramine D230 and GD230. Various measurements have been adopted to evaluate the self healing and anticorrosion performance. Results showed that the functional coating with a ratio of 8:2 for D230 to GD230 has satisfied both performances on the steel substrate. After immersion in 3 wt% NaCl solution for 120 days, the impedance value of functional coating still remains about 1010 Ω cm2. After the coating was scratched and immersion for 96 h, the impedance value of functional coating increased by about two orders of magnitude compared to that in blank coating. Mechanical testing and theoretical calculations were used to support dynamic crosslinking model to reveal the self-healing mechanism.

Preparation and Performance Study of Ultraviolet-Responsive Self-Healing Epoxy Asphalt.

In this study, a self-healing epoxy asphalt material was developed by incorporating coumarin groups. This material achieved microcrack self-repair under UV irradiation at 50 °C. Fluorescence microscopy observations and mechanical performance tests demonstrated significant advantages in crack filling and mechanical property recovery after repair, with the fracture toughness of the repaired epoxy asphalt reaching 69% of that in its original state. Furthermore, the synergistic effect of temperature and UV irradiation in the self-healing process enhanced the material's durability and service life. This research offers new insights and methods for developing more durable and long-lasting self-healing asphalt materials, showcasing the great potential of smart materials in infrastructure applications.

A self-healing epoxy coating realized by 2-chloromethylbenzimidazole loading MIL-88

A self-healing epoxy coating realized by 2-chloromethylbenzimidazole loading MIL-88

A bi-functional self-healing epoxy composite coating based on coordinated functionalized attapulgite/graphene oxide

Applications for graphene oxide (GO) in the field of corrosion protection will be severely constrained by the material’s poor dispersion and compatibility with epoxy resins, as well as the absence of self-healing corrosion protection in GO-based epoxy coatings. In this work, we developed a bi-functional 2-mercaptobenzothiazole (MBT) inhibitor-encapsulating GO-based nanocomposite (GAM) with pH-responsive release by implanting attapulgite (ATP) nanorods on the surface of GO. Additionally, GO-based nanocomposite can form covalent connections with epoxy resins and be evenly distributed in epoxy film via a ring opening process. Moreover, improved epoxy film compatibility and dispersion result in elevated mechanical strength and better impermeability, which prevent corrosion in both the active and passive modes. The corrosion resistance of GAM self-healing coating increased as the submersion period exceeded 24 h up to 0.54 M Ω cm2, resulting in the release of MBT inhibitor to form a passivation film at the defective region. Moreover, the improved charge transfer resistance (Rct) and the coating’s resistance to corrosive species (Rc) attribute to the self-healing ability of the GAM coating. The incorporation of GAM (2 %) nanocomposites into epoxy films enables long-term protection of AA2024-T3 by combining passive and self-healing corrosion prevention.

Self-Healing and Recyclable Castor Oil-Based Epoxy Vitrimer Based on Dual Dynamic Bonds of Disulfide and Ester Bonds

Self-Healing and Recyclable Castor Oil-Based Epoxy Vitrimer Based on Dual Dynamic Bonds of Disulfide and Ester Bonds

Effect of ZrO2 nanoparticles on the self-lubrication behavior of the linseed oil-loaded microcapsule/ epoxy composite coatings

Smart polymeric coatings play a crucial role in protecting steel surfaces from corrosion and wear. One of progressive smart behavior is self-healing behavior especially in self-healing epoxy coatings. Creating or improving the second smart behavior is known as a new trend for these smart materials. This study aims to investigate the effects of ZrO2 nanoparticles on the self-lubricating behavior as the second smart behavior of the linseed oil-loaded microcapsule/epoxy composite coatings. To do so, the in-situ polymerization method was used for the synthesis of linseed oil-loaded microcapsule. Results showed that the average size of prepared linseed oil-loaded microcapsules was 563 nm. The composite coatings were prepared by different content of ZrO2 nanoparticles (0, 3, 6, 9, 12, and 15 wt%) and constant content of linseed oil-loaded microcapsules (5 wt%). The tribological performance of samples was studied using pin-on-disk test. The worn surface of the samples was also studied using field emission scanning electron microscope (FESEM) images. Results proved that the frictional coefficient and wear rate of the samples were significantly decreased by increasing the concentrations of the ZrO2 nanoparticles up to 9 wt%. The lowest friction coefficient and wear rate values of 0.085 and 0.142 × 10−6 mm3/Nm were obtained for 5 wt% linseed oil-loaded microcapsules/epoxy with 9 wt% ZrO2 which were about 82 % and 88 % lower than those of pure epoxy coating.

Fabrication of photothermal responsive dual-chamber microcapsules for self-healing epoxy anticorrosion coatings

It has been urgent that timely repair of microdamage generated during long-term service of metal insulation coatings. Hereby, we developed a novel self-healing dual-chamber microcapsule with particle size about 5 μm, in which furfuryl amine modified polystyrene-acrylic acid (PSAF) as shell material and photosensitizer Carbon dots (CDs) as Pickering emulsifier. The synthesized materials were characterized analytically, FTIR and DSC demonstrated the simultaneously existence of healing agent and curing agent in the resultant dual-chamber microcapsule. Experiments also showed microcapsules exhibited satisfying storage stability more than 20 d at room temperature as well as thermogenesis effect that allowing temperature of epoxy composite materials raised to 50 °C in 60s and fractures to be effectively minimized in time. The scratch tensile measurement results demonstrated that epoxy resin composites incorporated with 2 wt% microcapsules exhibited the optimal strength self-healing efficiency, modulus, toughness and anti-fatigue performance. Furthermore, surface characterization and EIS analysis also confirmed the long-lasting healing effect of EP/MC2% complex coating with outstanding corrosion resistance. Therefore, the photothermal responsive dual-chamber microcapsule designed in this work has application as self-healing material especially epoxy anti-corrosion coating.

Self-healing epoxy coatings via microencapsulation of aromatic diisocyanate in lignin stabilized Pickering emulsions

Isocyanate-filled microcapsules are gaining increased attention for their role in developing self-healing materials, thereby reducing maintenance costs and increasing polymer durability. Nevertheless, microencapsulating highly reactive -NCO groups remains a challenging task in the literature. Likewise, considerable efforts have been directed towards developing polymers from renewable and biobased sources, which could also be applied to microcapsule synthesis. In this work, lignin, an abundant biopolymer, was used as a solid stabilizer for oil-in-water (O/W) interfaces, enabling the encapsulation of highly reactive isocyanate. Hybrid polyurethane/polyurea microcapsules containing reactive methylenediphenyl diisocyanate (MDI) were obtained via optimized O/W Pickering emulsions using lignin for system stabilization. This optimized process facilitated shell formation via the reaction of diisocyanate with lignin and water, eliminating the need for additional chain extenders. Scanning electron microscopy revealed the formation of spherical and rough microcapsules, while infrared spectroscopy confirmed the presence of residual free -NCO groups, indicating effective encapsulation of MDI. Additionally, a core -NCO concentration of 11 wt% was confirmed by titration. The microcapsules were further assessed as components in self-healing epoxy coatings. Their incorporation resulted in the retardation of corrosion on a low carbon steel panel after 72 h of submersion in a saline solution. Electrochemical impedance spectroscopy (EIS) confirmed a significant increase of approximated 620% in impedance modulus after 83 days of immersion in a 3.5 wt% NaCl solution, compared to the neat epoxy coating. These findings suggest a promising technological application of this material for the advancement of self-healing epoxy-based coatings and composites.

Machine learning assisted discovery of high-efficiency self-healing epoxy coating for corrosion protection

Machine learning is a powerful means for the rapid development of high-performance functional materials. In this study, we presented a machine learning workflow for predicting the corrosion resistance of a self-healing epoxy coating containing ZIF-8@Ca microfillers. The orthogonal Latin square method was used to investigate the effects of the molecular weight of the polyetheramine curing agent, molar ratio of polyetheramine to epoxy, molar content of the hydrogen bond unit (UPy-D400), and mass content of the solid microfillers (ZIF-8@Ca microfillers) on the low impedance modulus (lg|Z|0.01Hz) values of the scratched coatings, generating 32 initial datasets. The machine learning workflow was divided into two stages: In stage I, five models were compared and the random forest (RF) model was selected for the active learning. After 5 cycles of active learning, the RF model achieved good prediction accuracy: coefficient of determination (R2) = 0.709, mean absolute percentage error (MAPE) = 0.081, root mean square error (RMSE) = 0.685 (lg(Ω·cm2)). In stage II, the best coating formulation was identified by Bayesian optimization. Finally, the electrochemical impedance spectroscopy (EIS) results showed that compared with the intact coating ((4.63 ± 2.08) × 1011 Ω·cm2), the |Z|0.01Hz value of the repaired coating was as high as (4.40 ± 2.04) × 1011 Ω·cm2. Besides, the repaired coating showed minimal corrosion and 3.3% of adhesion loss after 60 days of neutral salt spray testing.

Preparation of fully epoxy resin microcapsules and their application in self-healing epoxy anti-corrosion coatings

Herein, an innovative self-healing epoxy coating with outstanding corrosion resistance has been developed. The self-healing capability of the coating is achieved by embedding microcapsules, comprising of solidified epoxy resin as the outer layer and liquid epoxy resin as the inner content. The chemical composition of the microcapsule wall is identical to that of the coating substrate, it is equivalent to injecting the liquid repair agent directly into the coating. Remarkably, due to the absence of any additional components in the coating system, the microcapsules seamlessly integrate with the resin matrix of the coating, showcasing exceptional compatibility.

Biohybrid microcapsules based on electrosprayed CS-immobilized nanoZrV for self-healing epoxy coating development.

In this work, zirconium vanadate nanoparticles were immobilized into chitosan using a facile electrospraying technique to produce CS-ZrV hybrid microcapsules for the development of a self-healing coating. Upon assessment, hybrid microcapsules possessed desirable properties with a mean particle size of 319 μm, maintaining good thermal stability of ∼55% at 700 °C, and were subsequently incorporated into an epoxy resin to develop a biocompatible self-healing coating, CZVEx, for carbon steel corrosion protection. Scratched samples of self-healing and control coatings were analyzed in a corrosion medium of 3.5 wt% aqueous NaCl. SEM images of the scratched coating sample, after days of immersion, revealed healing of defects through the appearance of an epoxide gel-like substance due to the release of polymeric vanadate that reacted with corrosion agents, resulting in polymerization of vanadium hydrates and subsequent self-healing, validated by the proposed mechanism of self-healing. Electrochemical impedance spectroscopy analysis further confirmed CZVEx coating possessed excellent self-healing capabilities through a significant impedance rise from 4.48 × 105 to 5.52 × 105 (ohm cm2) between the 7th and 14th day of immersion. Furthermore, comparative polarization assessment of coating samples with/without defects indicated the accuracy of EIS for self-healing analysis, and showed the sample with no defect was only 2.6 times more corrosion resistant than the scratched coating, as against bare steel substrate that was 22 times less resistant, revealing superior self-healing anticorrosion properties of the coating.

Reprocessed, shape-memory and self-healing robust epoxy resin by hindered urea bond

Given the fossil fuel energy crisis and serious environmental pollution in recent years, one way to alleviate the problem is to introduce dynamic covalent chemistry into thermosetting resins to give the material processable and recyclable properties, creating a new type of eco-friendly material. Hindered urea bonds can undergo reversible exchange reactions at high temperatures to decompose into amine and isocyanate. This reversible addition reaction is currently a prominent research focus in the development of reprocessable thermosets. In this work, we synthesize a novel curing agent with hindered urea bonds without any catalysts. Then characterize the resulting epoxy vitrimers based on hindered urea bond (HUG-EP) using FT-IR and 1H NMR, confirming the successful introduction of hindered urea bonds into the epoxy resin. A variety of tests are carried out, such as those to assess thermal stability, swelling, shape-memory, re-processability and tensile strength. The results demonstrate that HUG-EP can rapidly self-healed within 20 min at 160 °C, with the tensile strength was maintained at 87.15 % of the original during the welding experiments. Furthermore, it can also be reprocessed by hot-pressing several times at 160 °C. Thus, the introduction of hindered urea bonds into the crosslinked network proves to be an effective and practicable approach for producing thermosetting resins with reprocessing, self-healing, and shape memory capabilities.

Highly Thermal Stable, Stiff, and Recyclable Self-Healing Epoxy Based on Diels–Alder Reaction

Highly Thermal Stable, Stiff, and Recyclable Self-Healing Epoxy Based on Diels–Alder Reaction

Electric tree intrinsic self-healing epoxy insulating materials based on disulfide bond

Epoxy resin is one of the most commonly used insulating materials for electricians. Nevertheless, the emergence of localized damage or subtle microcracks within the material poses a formidable challenge in terms of detection and subsequent repair. The safe operation of power equipment is seriously jeopardized. In this study, driven by the need for self-healing insulating materials in power equipment applications, the successful synthesis of high-performance epoxy insulating materials featuring varying disulfide bond contents was achieved. Mechanical properties such as tensile strength and elongation at the break of epoxy insulations are enhanced by small amounts of disulfide bond. While an elevated content of disulfide bond diminishes the heat resistance and electrical characteristics of epoxy insulating materials, it is noteworthy that the prerequisites of epoxy resins for electrical applications remain adequately fulfilled. The results of the mechanical damage Self-healing test showed that the optimal repair efficiency reached 81.23 %. Simultaneously, the differentiation of electric tree branches can be inhibited by a disulfide bond. The diminishment of electric tree damage extent within epoxy resin is optimized, and the impairments of electric trees are repaired. Grounded in a disulfide bond, the viability of utilizing self-healing epoxy resins as insulating materials for electrical equipment is substantiated in this paper.

Self-healing carboxylic acid-cured epoxy networks driven by the cyclodextrin–cyclohexane host–guest interaction

Self-healing carboxylic acid-cured epoxy networks driven by the cyclodextrin–cyclohexane host–guest interaction

A Self-Healing Thermoset Epoxy Modulated by Dynamic Boronic Ester for Powder Coating.

Thermoset powder coatings exhibit distinctive characteristics such as remarkable hardness and exceptional resistance to corrosion. In contrast to conventional paints, powder coatings are environmentally friendly due to the absence of volatile organic compounds (VOCs). However, their irreversible cross-linking structures limit their chain segment mobility, preventing polymers from autonomously repairing cracks. Dynamic cross-linking networks have garnered attention for their remarkable self-healing capabilities, facilitated by rapid internal bond exchange. Herein, we introduce an innovative method for synthesizing thermoset epoxy containing boronic ester moieties which could prolong the life of the powder coating. The epoxy resin system relies on the incorporation of two curing agents: one featuring small-molecule diamines with boronic bonds and the other a modified polyurethane prepolymer. A state of equilibrium in mechanical properties was achieved via precise manipulation of the proportions of these agents, with the epoxy composite exhibiting a fracture stress of 67.95 MPa while maintaining a stable glass transition temperature (Tg) of 51.39 °C. This imparts remarkable self-healing ability to the coating surface, capable of returning to its original state even after undergoing 1000 cycles of rubbing (using 1200-grit abrasive paper). Furthermore, the introduction of carbon nanotube nanoparticles enabled non-contact sequential self-healing. Subsequently, we introduce this method into powder coatings of different materials. Therefore, this work provides a strategy to develop functional interior decoration and ensure its potential for broad-ranging applications, such as aerospace, transportation, and other fields.

Corrosion control by self-healing epoxy coatings

Corrosion control by self-healing epoxy coatings

Re-Assemblable, Recyclable, and Self-Healing Epoxy Resin Adhesive Based on Dynamic Boronic Esters.

Thermosetting adhesives are commonly utilized in various applications. However, covalent cross-linked networks prevent thermosetting adhesives from being re-assembled, which necessitates higher machining precision. Additionally, the primary raw materials used in adhesive preparation are derived from non-renewable petroleum resources, which further constrain adhesive development. In this study, a recyclable adhesive was developed by incorporating dynamic boronic esters into epoxy resin derived from soybean oil. The successful synthesis of epoxidized soybean oil and boronic esters was confirmed through the analysis of proton nuclear magnetic resonance spectra and differential scanning calorimetry results. Swelling tests and tensile curves demonstrated the presence of covalently cross-linked networks. Self-healing and reprocessing experiments indicated that the cross-linked network topology could be re-assembled under mild conditions.