RESUMEN

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.

RESUMEN

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.

RESUMEN

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 (Tg) and are inadequate for the repair of advanced composites. Because of their low Tg, 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 (Tg) of the epoxy/microcapsule composite was greater than the Tg 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.

RESUMEN

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.

RESUMEN

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.

Asunto(s)

Cápsulas/síntesis química , Formaldehído/síntesis química , Polímeros/síntesis química , Cápsulas/química , Técnicas de Química Sintética , Composición de Medicamentos , Formaldehído/química , Concentración de Iones de Hidrógeno , Indenos/administración & dosificación , Tamaño de la Partícula , Polimerizacion , Polímeros/química

RESUMEN

Cadmium is a heavy metal toxic that enters water resources through industrial, household, agricultural waste and non-sanitary landfill of urban and industrial wastes. Pollution of water resources by cadmium increases incidence of diseases including Itai-Itai, kidney disorders, cancer, chromosome effects and kidney tubular damages in low exposures. The aim of this study is to study the efficiency of a new poly urea-formaldehyde adsorbent in the removal cadmium ions from aqueous solutions. The effect of different variables such as initial pH, contact time, initial concentration of cadmium and test of real wastewater samples were evaluated. In addition, laboratory data of cadmium adsorption by urea-formaldehyde adsorbent were matched to Langmuir, Freundlich and Temkin isotherm models. The results of the study showed that maximum adsorption capacity obtained by Langmuir model was 76.3 mg/g at pH = 5.5. Laboratory adsorption data matched mostly by Freundlich isotherm model (R2 =0.999) which indicates that adsorption of cadmium ions on heterogenic surfaces of poly urea-formaldehyde happens by chemical adsorption mechanism. Generally, the results of the study showed that new poly urea-formaldehyde adsorbent can be efficiently used to remove highly concentrated cadmium ions from aqueous solutions.