Search Results (16)

The development of self-healing coatings represents a promising approach to enhance the durability of metal substrates exposed to corrosive environments, demanding thorough in situ investigations. In this study, poly(urea–formaldehyde–melamine) (PUF) microcapsules containing linseed oil (LO) were synthesized via in situ polymerization to act as healing agents in protective coatings. The microcapsules were characterized using scanning electron microscopy (SEM), optical microscopy (OM), Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The capsules exhibited a regular spherical morphology with an average diameter of 96 µm and an LO encapsulation efficiency of 81 wt%. TGA confirmed their thermal stability up to 200 °C, while FTIR verified the successful encapsulation of LO. For performance evaluation, 10 wt% of the microcapsules was incorporated into an epoxy matrix and applied to carbon steel. Corrosion resistance was evaluated using electrochemical impedance spectroscopy (EIS) in 0.1 mol/L of NaCl solution over 500 h. The coating with microcapsules exhibited a |Z|_0.01 of 10⁶ Ω·cm², higher than the 10⁴ Ω·cm² observed for the coating without microcapsules, indicating improved barrier properties. Raman spectroscopy confirmed the auto-oxidation of LO at damaged areas, evidencing the self-healing mechanism. Although full barrier recovery was not achieved, the system effectively delayed corrosion progression. Full article

This article proposes the synthesis and characterization of (triethylene glycol dimethacrylate–N,N-dihydroxyethyl-p-toluidine) TEGDMA-DHEPT self-healing microcapsules for their inclusion in dental composite formulations. The obtaining method is the in situ emulsion polymerization of the (poly urea-formaldehyde) (PUF) coatings. The microcapsules were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), atomic force microscopy (AFM), high-performance liquid chromatography (HPLC), and low-field nuclear magnetic resonance (NMR) techniques. The optimal formation of uniform microcapsules is achieved at a stirring speed of 800 rpm and centrifugation is no longer necessary. HPLC demonstrates that the microcapsules formed at 800 rpm show a better control of liquid release than the heterogeneous ones obtained at a lower stirring speed. The centrifuged samples have rounded shapes, with dimensions between 80 and 800 nm, while the non-centrifuged samples are more uniform, with a spherical shape and dimensions of approximately 800 nm. Full article

Dental resin composites are widely used in clinical settings but often face longevity issues due to the development and accumulation of microcracks, which eventually lead to larger cracks and restoration failure. The incorporation of microcapsules into these resins has been explored to introduce self-healing capability, potentially extending the lifespan of the restorations. This study aims to enhance the performance of self-healing dental resins by optimizing the microcapsules–resin matrix physicochemical interactions. Poly(urea–formaldehyde) (PUF) microcapsules were reinforced with melamine and subsequently subjected to surface functionalization with 3-aminopropyltriethoxysilane (APTES) and (3-mercaptopropyl)trimethoxysilane (MPTMS). Additionally, microcapsules were functionalized with a bilayer approach, incorporating tetraethyl orthosilicate (TEOS) with either APTES or MPTMS. X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA) confirmed an increased Si:C ratio from 0.006 to 0.165. The functionalization process did not adversely affect the structure of the microcapsules or their healing agent volume. Compared to PUF controls, the functionalized microcapsules demonstrated enhanced healing efficiency, with TEOS/MPTMS-functionalized microcapsules showing the highest performance, showing a toughness recovery of up to 35%. This work introduces a novel approach to functionalization of microcapsules by employing advanced silanizing agents such as APTES and MPTMS, and pioneering bilayer functionalization protocols through their combination with TEOS. Full article

Cargo encapsulation through emulsion-based methods has been pondered over the years. Although several microemulsification techniques have been employed for the microcapsule’s synthesis, there are still no clear guidelines regarding the suitability of one technique over the others or the impacts on the morphological and physicochemical stability of the final particles. Therefore, in this systematic study, we investigated the influence of synthesis parameters on the fabrication of emulsion-based microcapsules concerning morphological and physicochemical properties. Using poly(urea-formaldehyde) (PUF) microcapsules as a model system, and after determining the optimal core/shell ratio, we tested three different microemulsification techniques (magnetic stirring, ultrasonication, and mechanical stirring) and two different cargo types (100% TEGDMA (Triethylene glycol dimethacrylate) and 80% TEGDMA + 20% DMAM (N,N-Dimethylacrylamide)). The resulting microcapsules were characterized via optical and scanning electron microscopies, followed by size distribution analysis. The encapsulation efficiency was obtained through the extraction method, and the percentage reaction yield was calculated. Physicochemical properties were assessed by incubating the microcapsules under different osmotic pressures for 1 day and 1, 2, or 4 weeks. The data were analyzed statistically with one-way ANOVA and Tukey’s tests (α = 0.05). Overall, the mechanical stirring resulted in the most homogeneous and stable microcapsules, with an increased reaction yield from 100% to 50% in comparison with ultrasonication and magnetic methods, respectively. The average microcapsule diameter ranged from 5 to 450 µm, with the smallest ones in the ultrasonication and the largest ones in the magnetic stirring groups. The water affinities of the encapsulated cargo influenced the microcapsule formation and stability, with the incorporation of DMAM leading to more homogeneous and stable microcapsules. Environmental osmotic pressure led to cargo loss or the selective swelling of the shells. In summary, this systematic investigation provides insights and highlights commonly overlooked factors that can influence microcapsule fabrication and guide the choice based on a diligent analysis of therapeutic niche requirements. Full article

Tung oil (TO) microcapsules (MCs) with a poly(urea-formaldehyde) (PUF) shell were synthesized via one-step in situ polymerization, with the addition of graphene nanoplatelets (GNPs) (1–5 wt. %). The synergistic effects of emulsifiers between gelatin (gel) and Tween 80 were observed, with gel chosen to formulate the MCs due to its enhanced droplet stability. SEM images then displayed an increased shell roughness of the TO-GNP MCs in comparison to the pure TO MCs due to the GNP species on the shell. At the same time, high-resolution transmission electron microscopy (TEM) images also confirmed the presence of GNPs on the outer layer of the MCs, with the stacked graphene layers composed of 5–7 layers with an interlayer distance of ~0.37 nm. Cross-sectional TEM imaging of the MCs also confirmed the successful encapsulation of the GNPs in the core of the MCs. Micromanipulation measurements displayed that the 5% GNPs increased the toughness by 71% compared to the pure TO MCs, due to the reduction in the fractional free volume of the core material. When the MCs were dispersed in an epoxy coating and applied on a metallic substrate, excellent healing capacities of up to 93% were observed for the 5% GNP samples, and 87% for the pure TO MC coatings. The coatings also exhibited excellent corrosion resistance for all samples up to 7 days, with the GNP samples offering a more strenuous path for the corrosive agents. Full article

The common, commercial reversible thermochromic (RT) melamine–formaldehyde resin microcapsules containing formaldehyde are very harmful to human health. To address this issue, we successfully prepared a novel formaldehyde-free microcapsule via interfacial polymerization using RT compositions as the core and poly(urethane-urea) (PUU) as the shell. The core material consisted of a color former (crystal violet lactone), a developer (bisphenol AF), and a solvent (methyl stearate). To optimize the synthesis of the microcapsules, an L₉ (3⁴) orthogonal design and single-factor experiments were employed to analyze the effects of four factors (N3300-to-L75 shell material mass ratio, core-to-shell material mass ratio, emulsifier concentration, and shear rate during emulsification) on the encapsulation efficiency. The results showed that the optimal parameter values were as follows: a shear rate of 2500 rpm, N3300-to-L75 shell material mass ratio of 1:4, core-to-shell material mass ratio of 11:5, and emulsifier concentration of 3.5%. The influence of the shear rate on the particle size and distribution, surface morphology, dispersibility, and reversible thermochromic properties of the microcapsules was investigated. Furthermore, analyses on the phase-change characteristics, thermal stability, ultraviolet aging, and solvent and acid–base resistances of the microcapsules were conducted systematically. Finally, a reversible thermochromic mark containing the RTPUU microcapsules was designed and fabricated, which could be used against falsification. Moreover, these RTPUU microcapsules can be potentially used for anticounterfeiting applications. Full article

Smart coatings and smart polymers have been garnering great interest in recent times due to their novel characteristics, such as being self-restoring, self-cleaning, and self-healing. However, most self-healing materials have a low glass transition temperature (T_g) and are inadequate for the repair of advanced composites. Because of their low T_g, the conventional self-healing materials plasticize and weaken the composites. In this study, moderate to high temperature self-healing microcapsules, capable of healing and thus stopping crack propagation, are prepared. The microcapsules were prepared using a two-step process involving the synthesis of poly(urea formaldehyde) (PUF) prepolymer, followed by the encapsulation of hexamethylene diisocyanate (HDI) in an oil-in-water emulsion to form a crosslinked PUF shell. Diisocyanates are of particular interest as self-healing encapsulants because of their diversity of structure and fast rate of hydrolysis. Successful encapsulation was verified by Fourier transform infrared spectroscopy (FTIR) and optical microscopy. Thermogravimetric analysis (TGA) was used to characterize the thermal properties of microcapsules. The onset temperature for microcapsule degradation varied from 155 °C to 195 °C. Dynamic mechanical analysis (DMA) was used to determine the thermomechanical response of microcapsule/epoxy films. DMA showed that the glass transition temperature (T_g) of the epoxy/microcapsule composite was greater than the T_g for neat epoxy and varied between 34 and 65 °C. The TGA analysis of the epoxy/microcapsule composite shows that the thermal stability and char retention of the epoxy/microcapsule composite increased and the low temperature decomposition peak at 150 °C, associated with the microcapsule, disappeared after the DMA test, indicating the occurrence of a reaction between HDI and the epoxy to form a crosslinked polyurea network structure. Full article

In this work, tung oil was utilised as a catalyst-free self-healing agent, and an in-situ polymerization process was applied to encapsulate the tung oil core with a poly(urea-formaldehyde) (PUF) shell. The conventional poly(ethylene-alt-maleic-anhydride) (PEMA) polymer was compared to a more naturally abundant gelatin (GEL) emulsifier to compare the microcapsules’ barrier, morphological, thermal, and chemical properties, and the crystalline nature of the shell material. GEL emulsifiers produced microcapsules with a higher payload (96.5%), yield (28.9%), and encapsulation efficiency (61.7%) compared to PEMA (90.8%, 28.6% and 52.6%, respectively). Optical and electron microscopy imaging indicated a more uniform morphology for the GEL samples. The thermal decomposition measurements indicated that GEL decomposed to a value 7% lower than that of PEMA, which was suggested to be attributed to the much thinner shell materials that the GEL samples produced. An innovative and novel focused ion beam (FIB) milling method was exerted on the GEL sample, confirming the storage and release of the active tung oil material upon rupturing. The samples with GEL conveyed a higher healing efficiency of 91%, compared to PEMA’s 63%, and the GEL samples also conveyed higher levels of corrosion resistance. Full article

The activities of this paper were focused on an in-situ fabrication process for producing two self-healing systems containing dicyclopentadiene and 5-ethylidene-2-norbornene monomers encapsulated in a urea-formaldehyde shell and integration methods applied in the epoxy matrix to analyse and compare the influences of their integration into the neat epoxy matrix. The self-healing systems were first synthesized according to a literature review, and subsequently, an optimization process was conducted for the fabrication process. Neat epoxy specimens were fabricated as reference specimens and subjected to flexural tests. Several integration methods for incorporating the self-healing systems into the epoxy resin were investigated. The optimal method presenting the best dispersion of the healing system was achieved by reducing the viscosity of the epoxy matrix with 10 vol % acetone solution, the addition of a microcapsule in the matrix, and homogenization at 60 °C at 100 rpm. Thermal analysis was performed in order to observe the mass loss obtained with an increasing temperature and phase changes for both poly-urea-formaldehyde (PUF)-dicyclopentadiene (DCPD) and melamine-urea-formaldehyde (MUF)-5-ethylidene-2-norbornene (ENB) systems. The thermogravimetric analysis performed for the PUF-DCPD system indicates a total loss of mass in the range of 30–500 °C of 72.604% and for the MUF-ENB system, indicates a total mass loss in the range of 30–500 °C of 74.093%. Three-point bending tests showed higher mechanical properties for PUF-DCPD (80%) than MUF-ENB (40%) compared to the neat epoxy systems. Numerical simulations were performed to obtain a better understanding of the microcapsule behavior when embedded in an epoxy matrix. Full article

With the increasing demands to better the marine environment, environmentally friendly anti-fouling coatings have attracted attention from society. Adding hydrolyzable microcapsules without toxin to paints is a very useful and safe method to get bionic anti-fouling coatings with a micro-nano surface structure. Based on this trend, a form of environment-friendly microcapsules were prepared through mini-emulsion polymerization. The target microcapsules had a poly(urea-formaldehyde) (PUF) shell and a mixed core of silicone oil and capsaicin. Additionally, the microcapsules were introduced into zinc acrylate resin to obtain bionic anti-fouling coatings with micro-nano morphology. The effects of polyvinyl alcohol (PVA) molecular weight, stirring rate, and temperature on the morphology of the microcapsules were studied by optical microscopy (OM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that spherical nanoparticles with smooth surfaces were obtained, and the mean diameter was approximately 1.38 μm when the molecular weight of PVA was 77 K, the stirring rate was 600 rpm and the temperature was 55 °C. Fourier-transform infrared spectra (FTIR) results showed that the silicone oil and capsaicin were successfully encapsulated, the core materials of the microcapsules reached 72.37% and the yield of microcapsules was 68.91% by the Soxhlet method. Furthermore, the hydrophobicity, corrosion resistance and anti-fouling performance of the coatings were evaluated by the water contact angle, electrochemical and real-sea tests. The results indicated that the anti-fouling coatings had excellent hydrophobicity and anti-fouling performance due to the micro-nano convex structure and the release of core materials. Encouragingly, the anti-fouling coatings show excellent and long-term anti-fouling performance, which is expected to be widely applied in marine anti-fouling coatings. Full article

Self-healing materials can promote the sustainable reuse of resources. Poly (urea-formaldehyde) (PUF) microcapsules can be incorporated into dielectric materials for self-healing. However, the mechanical properties of PUF microcapsules need to be improved due to insufficient hardness. In this paper, PUF models incorporated with nano-SiO₂ of different filler concentrations (0, 2.6, 3.7, 5.3, 6.7, 7.9 wt.%) were designed. The density, the fractional free volume, and the mechanical properties of the PUF-SiO₂ models were analyzed at an atomic level based on molecular dynamics simulation. The interfacial interaction model of PUF on the SiO₂ surface was also constructed to further investigate the interaction mechanisms. The results showed that the incorporation of nano-SiO₂ had a significant effect on the mechanical properties of PUF. Density increased, fractional free volume decreased, and mechanical properties of the PUF materials were gradually enhanced with the increase of nano-SiO₂ concentration. This trend was also confirmed by experimental tests. By analyzing the internal mechanism of the PUF–SiO₂ interfacial interaction, it was found that hydrogen bonds play a major role in the interaction between PUF and nano-SiO₂. Moreover, hydrogen bonds can be formed between the polar atoms of the PUF chain and the hydroxyl groups (–OH) as well as O atoms on the surface of SiO₂. Hydrogen bonds interactions are involved in adsorption of PUF chains on the SiO₂ surface, reducing the distance between PUF chains and making the system denser, thus enhancing the mechanical properties of PUF materials. Full article

Previous research has demonstred that microencapsulated phase change materials (MEPCMs) could significantly increase the energy storage density of solar thermal energy storage (TES) systems. Compared with traditional phase change materials (PCMs), MEPCMs have many advantages since they can limit their exposure to the surrounding environment, enlarge the heat transfer area, and maintain the volume as the phase change occurs. In this study, a new MEPCM for solar TES systems is developed by encapsulation of paraffin wax with poly (urea formaldehyde) (PUF). The experimental results revealed that agglomeration of MEPCM particles occurred during the encapsulation process which affected the uniformity of the particle size distribution profile when sodium dodecyl sulfate was used as an emulsifier. The differential scanning calorimetric (DSC) analysis results showed that the melting temperatures were slightly increased by 0.14–0.72 °C after encapsulation. A thermogravimetric (TG) test showed that the sample weight decreased while the weight loss starting temperature was slightly increased after encapsulation. Overall, the sample UF-2, fabricated with the binary emulsifiers of Brij 35 and Brij 30 and 5% nucleating agent, resulted in good particle dispersion and shell integrity, higher core material content and encapsulation efficiency, as well as improved thermal stability. Full article

We report the development of an extrinsic, self-healing coating system that shows no fluorescence from intact coating, yellowish fluorescence in cracked regions, and greenish fluorescence in healed regions, thus allowing separate monitoring of cracking and healing of coatings. This fluorescence-monitoring self-healing system consisted of a top coating and an epoxy matrix resin containing mixed dye loaded in a single microcapsule. The dye-loaded microcapsules consisted of a poly(urea-formaldehyde) shell encapsulating a healing agent containing methacryloxypropyl-terminated polydimethylsiloxane (MAT-PDMS), styrene, a photo-initiator, and a mixture of two dyes: one that fluoresced only in the solid state (DCM) and a second that fluoresced dramatically in the solid than in the solution state (4-TPAE). A mixture of the healing agent, photo-initiator, and the two dyes was yellow due to fluorescence from DCM. On UV curing of this mixture, however, the color changed from yellow to green, and the fluorescence intensity increased due to fluorescence from 4-TPAE in the solid state. When a self-healing coating embedded with microcapsules containing the DCM/4-TPAE dye mixture was scratched, the damaged region exhibited a yellowish color that changed to green after healing. Thus, the self-healing system reported here allows separate monitoring of cracking and healing based on changes in fluorescence color. Full article

Paraffin, the most common phase change material, has been widely utilized as the core component in thermal energy storage in the form of microcapsules. In this study, semi-crystalline paraffin is capsulated into a poly(urea-formaldehyde) (PUF) shell by a two-step polymerization process. To obtain the microcapsule with good morphology and high latent heat, sodium chloride and crosslinker (a mixture of ammonium chloride and resorcinol with a weight ratio of 1:1) are incorporated and their addition amounts were optimized through differential scanning calorimetry (DSC) and SEM. The optimized microcapsules were obtained by adding 4 wt% sodium chloride, and 0.25 wt% crosslinker exhibits a diameter of several microns and a melting enthalpy of 110 J/g. This detailed study shows that sodium chloride strongly affects the morphology of paraffin emulsion by enlarging droplets, widening the size distribution, and enhancing the stability, which should be attributed to the enhancement of electric double layer strength. In addition, sodium chloride can weaken the Zeta potential of prepolymer and provides more opportunity for prepolymer to deposit on the surface of emulsion droplets. The two components in crosslinker play different roles in the polymerization process. Ammonium chloride reacts with prepolymers and reduces the pH of system, which can accelerate the curing process, while resorcinol probably participates in polymerization as a comonomer. Full article

Fracture and secondary caries are the primary reasons for the failure of dental restorations. To face this omnipresent problem, we report the formulation design and synthesis of a protein-resistant dental composite composed of 2-methacryloyloxyethyl phosphorylcholine (MPC) that also can self-repair damage and recover the load-bearing capability via microencapsulated triethylene glycol dimethacrylate (TEGDMA) and N,N-dihydroxy ethyl-p-toluidine (DHEPT). The bioactivity of the resulting MPC-microencapsulated TEGDMA-DHEPT was evaluated on protein adsorption through early bacterial attachment. Its mechanical properties were also investigated, including self-healing assessment. Microcapsules of poly (urea-formaldehyde) (PUF) were synthesized by incorporating a TEGDMA-DHEPT healing liquid. A set of composites that contained 7.5% of MPC, 10% of microcapsules, and without MPC/microcapsules were also prepared as controls. The two distinct characteristics of strong protein repellency and load-bearing recovery were achieved by the combined strategies. The novel dual composite with a combination of protein-repellent MPC and PUF microcapsules for restoring microcracks is a promising strategy for dental restorations to address the two main challenges of fracture and secondary caries. The new dual composite formulation design has the potential to improve the longevity of dental restorations significantly. Full article