Search Results (13)

The present article introduces a strategy for controlling oxidation and reduction reactions within polymer electrolyte membrane (PEM) networks as a means of enhancing storage capacity through the complexation of dissociated lithium cations with multifunctional groups of the polymer network. Specifically, co-polymer networks based on polysulfide (PS) and polyoxide (PO) precursors, photo-cured in the presence of succinonitrile (SCN) and lithium bis(trifluoro methane sulfonyl imide) (LiTFSI) salt, exhibited ionic conductivity on the order of mid 10⁻⁴ S/cm at ambient temperature in the 30/35/35 (weight %) composition. Lithium titanate (LTO, Li₄Ti₅O₁₂) electrode was chosen as an anode (i.e., a potential source of Li ions) against lithium iron phosphate (LFP, LiFePO₄) cathode in conjunction with polysulfide-co-polyoxide dual polyelectrolyte networks to control viscosity for 3D printability on conformal surfaces of drone and aeronautic vehicles. It was found that the PS-co-PO dual network-based polymer electrolyte containing SCN plasticizer and LiTFSI salt exhibited extra storage capacity (i.e., specific capacity of 44 mAh/g) with the overall specific capacity of 170 mAh/g (i.e., for the combined LTO electrode and PEM) initially that stabilized at 153 mAh/g after 50th cycles with a reasonable capacity retention of over 90% and Coulombic efficiency of over 99%. Of particular interest is the observation of the improved electrochemical performance of the polysulfide-co-polyoxide electrolyte dual-network relative to that of the polyoxide electrolyte single-network. Full article

Recently, photocurable coatings are being used frequently. However, it is worth mentioning that the use of photopolymerization has its drawbacks, especially in the case of curing coatings on three-dimensional surfaces and in places that are difficult to access for UV radiation. However, it is possible to develop a system in which UV technology and thermal methods for curing coatings can be combined. Moreover, the obtained resins are derived from low-viscosity epoxy resins or diglycidyl ethers, making them an ideal building material for photopolymerization-based three-dimensional printing techniques. Due to the need to improve this method, a series of epoxy (meth)acrylates containing both epoxy and (meth)acrylate groups were obtained via the addition of acrylic or methacrylic acid to epoxy resin, diglycydylether of bisphenol A epoxy resin (DGEBA), cyclohexane dimethanol diglycidyl ether (CHDMDE) and neopentyl glycol diglycidyl ether (NPDE). The structures of the synthesized copolymers were confirmed through spectroscopic analysis (FTIR) and studied regarding their nonvolatile matter content (NV) and acid values (PAVs), as well as their epoxy equivalent values (EEs). Due to the presence of both epoxy and double carbon–carbon pendant groups, two distinct mechanisms can be applied: cationic and radical. Hence, the obtained resins can be cured using UV radiation with thermally appropriate conditions and initiators. This type of method can be used as a solution to many problems currently encountered in using UV technology, such as failure to cure coatings in underexposed areas as well as deformation of coatings. Synthesized epoxy (meth)acrylate prepolymers were employed to formulate photocurable coating compositions. Furthermore, the curing process and properties of cured coatings were investigated regarding some structural factors and parameters. Among the synthesized materials, the most promising are those based on epoxy resin, characterized by their high glass transition temperature values and satisfactory functional properties. Full article

During the last decades, multicomponent photoinitiating systems have been the focus of intense research efforts, especially for the design of visible light photoinitiating systems. Although highly reactive three-component and even four-component photoinitiating systems have been designed, the complexity to elaborate such mixtures has incited researchers to design monocomponent Type II photoinitiators. Using this approach, the photosensitizer and the radical/cation generator can be combined within a unique molecule, greatly simplifying the elaboration of the photocurable resins. In this field, sulfonium salts are remarkable photoinitiators but these structures lack absorption in the visible range. Over the years, various structural modifications have been carried out in order to redshift their absorptions in the visible region. In this work, an overview of the different sulfonium salts activable under visible light and reported to date is proposed. Full article

The effect of semiconducting tungsten disulfide (WS₂) nanoparticles (NPs), functionalized by either methacryloxy, glycidyl, vinyl, or amino silanes, has been studied in photocuring of acrylate and epoxy resins (the latter photocured according to a cationic mechanism). The curing time, degree of curing (DC), thermal effects, and mechanical properties of the radiation-cured resins were investigated. X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) analyses confirmed that a silane coating was formed (1–4 nm) on the NPs’ surface having a thickness of 1–4 nm. Fourier transition infrared (FTIR) was used to determine the DC of the nanocomposite resin. The curing time of the epoxy resin, at 345–385 nm wavelength, was 10 to 20 s, while for acrylate, the curing time was 7.5 min, reaching 92% DC in epoxy and 84% in acrylate. The glass transition temperature (Tg) of the photocured acrylates in the presence of WS₂ NPs increased. In contrast to the acrylate, the epoxy displayed no significant variations of the Tg. It was found that the silane surface treatments enhanced the DC. Significant increases in impact resistance and enhancement in shear adhesion strength were observed when the NPs were treated with vinyl silane. A previous study has shown that the addition of WS₂ NPs at a concentration of 0.5 wt.% is the optimal loading for improving the resin’s mechanical properties. This study supports these earlier findings not only for the unmodified NPs but also for those functionalized with silane moieties. This study opens new vistas for the photocuring of resins and polymers in general when incorporating WS₂ NPs. Full article

Vitrimers brought new properties in thermosets by allowing their reshaping, self-healing, reprocessing, and network rearrangement without changing structural integrity. In this study, epoxidized castor oil (ECO) was successfully used for the straightforward synthesis of a bio-based solvent-free vitrimer. The synthesis was based on a UV-curing process, which proceeded at low temperatures in the absence of any solvents, and within a short time. Real time Fourier-transformed infrared spectroscopy and photo-DSC were exploited to monitor the cationic photocurable process. The UV-cured polymer networks were able to efficiently undergo thermo-activated bond exchange reactions due to the presence of dibutyl phosphate as a transesterification catalyst. Mechanical properties, thermal resistance, glass transition temperature, and stress relaxation were investigated as a function of the amount of transesterification catalyst. Mechanical properties were determined by both DMTA and tensile tests. Glass transition temperature (T_g) was evaluated by DMTA. Thermal stability was assessed by thermogravimetric analysis, whilst vitrimeric properties were studied by stress relaxation experiments. Overall, the ECO-based vitrimer showed high thermal resistance (up to 200 °C) and good mechanical properties (elastic modulus of about 10 MPa) and can therefore be considered as a promising starting point for obtaining more sustainable vitrimers. Full article

A series of difunctional epoxy methacrylate resins (EAs) containing at least one epoxy and at least one methacrylate group were synthesized by means of an addition reaction between epoxy-terminated diglycidyl ethers and methacrylic acid. In order to investigate the impact of polymer architecture on the course of addition reactions and further coating properties, several different types of diglycidyl ethers, i.e., linear, containing aliphatic or aromatic rings, with a short or polymeric backbone, were employed in the synthesis. The carboxyl–epoxide addition esterification reactions have been found to, in a relatively straightforward manner, control the extent of acrylation depending on the substrate feed ratio and reaction time. The structure of obtained pre-polymers was evaluated by FT-IR and NMR methods. At the same time, the extent of addition reactions was validated via quantitative analysis, including non-volatile matter content (NV), acid value (PAVs), and epoxy equivalent value (EE) analysis. The modification was carried out in a manner likely to create a compound with one epoxy and one carbon–carbon pendant group. Hence, due to the presence of both functionalities, it is possible to crosslink compositions based on synthesized EAs via two distinct mechanisms: (i) cationic polymerization or (ii) free-radical polymerization. Synthesized epoxy methacrylate pre-polymers were further employed for use in formulate photocurable coating compositions by the cationic or radical process. Furthermore, the photopolymerization behavior and properties of cured coatings were explored regarding some structural factors and parameters. The investigated polymeric materials cure in a short time to obtain coatings with good properties, which is why they can be successfully used to produce protective and decorative coatings for many industries. Full article

Even though there are many photocurable compositions that are cured by cationic photopolymerization mechanisms, UV curing generally consists of the formation of cross-linking covalent bonds between a resin and monomers via a photoinitiated free radical polymerization reaction, obtaining a three-dimensional polymer network. One of its many applications is in the refinish coatings market, where putties, primers and clear coats can be cured faster and more efficiently than with traditional curing. All these products contain the same essential components, which are resin, monomers and photoinitiators, the latter being the source of free radicals. They may also include additives used to achieve a certain consistency, but always taking into account the avoidance of damage to the UV curing—for example, by removing light from the innermost layers. Surface curing also has its challenges since it can be easily inhibited by oxygen, although this can be solved by adding scavengers such as amines or thiols, able to react with the otherwise inactive peroxy radicals and continue the propagation of the polymerization reaction. In this review article, we cover a broad analysis from the organic point of view to the industrial applications of this line of research, with a wide current and future range of uses. Full article

In this work, epoxy acrylate resin (EA) based on the industrial-grade bisphenol A-based epoxy resin (Ep6) and acrylic acid (AA) has been synthesized in order to develop hybrid resin comprising both epoxide group and reactive, terminal unsaturation. Obtained epoxy acrylate prepolymer was employed to formulate photocurable coating compositions containing, besides the EA binder, also cationic or radical photoinitiators. Hence, when cationic photoinitiators were applied, polyether-type polymer chains with pending acrylate groups were formed. In the case of free radical polymerization, epoxy acrylates certainly formed a polyacrylate backbone with pending epoxy groups. Owing to the presence of both epoxy and double carbon–carbon pendant groups, the reaction product exhibits photocrosslinking via two distinct mechanisms: (i) cationic ring-opening polymerization and (ii) free radical polymerization. Therefore, photopolymerization behavior of synthetized hybrid resin with various photoinitiators was determined via photo-differential scanning calorimetry (photo-DSC) and real-time infrared spectroscopy (RT-IR) methods, and properties of cured coatings were investigated. The performance of the following type of photoinitiators was tested in the cationic photopolymerization: diaryliodonium cations or triarylsulfonium cations, and the following type of photoinitiators were used to induce free radical photopolymerization: α-hydroxyketones, acylphosphine oxides, and their mixtures. Lastly, the basic physicomechanical properties of cured coatings, such as tack-free time, hardness, adhesion, gloss, and yellowness index, were evaluated. Some structural factors and parameters of cationic and radical photoinitiators and photopolymerization mechanisms affecting the epoxy acrylate hybrid coatings performance are discussed. Full article

In this work, a series of novel multifunctional epoxy (meth)acrylate resins based on a low-viscosity aliphatic triepoxide triglycidyl ether of trimethylolethane (TMETGE) and acrylic acid (AA) or methacrylic acid (MMA) have been synthesized. Thanks to the performed modification, the obtained prepolymers have both epoxides as well as carbon–carbon double bonds and differ in their amount. The obtained results indicate that the carboxyl-epoxide addition esterification occurs in the presence of a catalyst (triphenylphosphine) at a temperature of 90 °C, whilst the required degree of conversion can be achieved simply by varying both the reagents ratio and reaction time. The structure of synthesized copolymers was confirmed by spectroscopic analyses (FT-IR, ¹H NMR, ¹³C NMR) and studied regarding its nonvolatile matter content (NV), acid value (PAVs), as well as its epoxy equivalent value (EE). Due to the presence of both epoxy and double carbon–carbon pendant groups, one can apply two distinct mechanisms: (i) cationic ring-opening polymerization or (ii) free-radical polymerization to crosslink polymer chains. Synthesized epoxy (meth)acrylate prepolymers were further employed to formulate photocurable coating compositions. Hence, when cationic photoinitiators were applied, polyether-type polymer chains with pending acrylate or methacrylate groups were formed. In the case of free-radical polymerization, epoxy (meth)acrylates certainly formed a poly(meth)acrylate backbone with pending epoxy groups. Further, photopolymerization behavior and properties of cured coatings were investigated regarding some structural factors and parameters. Moreover, reaction rate coefficients of photo-cross-linking by both cationic ring-opening and free-radical photopolymerization of the received epoxy (meth)acrylate resins were determined via real-time infrared spectroscopy (RT-IR). Lastly, basic physicomechanical properties, such as tack-free time, hardness, adhesion, gloss, and yellowness index of cured coatings, were evaluated. Full article

Cardanol is a natural alkylphenolic compound derived from Cashew NutShell Liquid (CNSL), a non-food annually renewable raw material extracted from cashew nutshells. In the quest for sustainable materials, the curing of biobased monomers and prepolymers with environmentally friendly processes attracts increasing interest. Photopolymerization is considered to be a green technology owing to low energy requirements, room temperature operation with high reaction rates, and absence of solvents. In this work, we study the photocuring of a commercially available epoxidized cardanol, and explore its use in combination with microfibrillated cellulose (MFC) for the fabrication of fully biobased composites. Wet MFC mats were prepared by filtration, and then impregnated with the resin. The impregnated mats were then irradiated with ultraviolet (UV) light. Fourier Transform InfraRed (FT-IR) spectroscopy was used to investigate the photocuring of the epoxidized cardanol, and of the composites. The thermomechanical properties of the composites were assessed by thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. We confirmed that fully cured composites could be obtained, although a high photoinitiator concentration was needed, possibly due to a side reaction of the photoinitiator with MFC. Full article

Nanostructured hydroxyapatite (HA) is a new class of biocompatible fillers which has been recently utilized in bio hybrid materials by virtue of its excellent tissue bioactivity and biocompatibility. However, the need for higher thermal stability, solubility, surface bioactivity, radiopacity, and remineralization ability suggests a divalent cation substitution of HA for use in light curable dental restorative composites. In this work, structural and optical properties of Sr-doped hydroxyapatite were studied using first-principle calculations based on density functional theory (DFT). Next, Sr-doped hydroxyapatite (HA) was prepared via a new ionic liquid-assisted hydrothermal (ILH) route. Samples were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM)/energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), dynamic light scattering (DLS), Brunauer–Emmett–Teller (BET) surface area analysis, and cell viability. The obtained experimental data showed that the nucleation and crystal growth process controlled by [BMIM]Br molecules results in uniform products with small and regular particles and high specific surface areas. Finally, cytotoxicity tests showed that the as-prepared Sr-doped HA nanoparticles have good biocompatibility (≥91%), confirming their potential for use in photo-curable dental restorative composites. Full article

In this work, a novel boehmite (BA)-embedded organic/inorganic nanocomposite coating based on cycloaliphatic epoxy oligosiloxane (CEOS) resin was fabricated applying UV-induced cationic polymerization. The main changes of the material behavior caused by the nanofiller were investigated with regard to its photocuring kinetics, thermal stability, and glass transition. The role of the particle surface was of particular interest, thus, unmodified nanoparticles (HP14) and particles modified with p-toluenesulfonic acid (OS1) were incorporated into a CEOS matrix in the concentration range of 1–10 wt.%. Resulting nanocomposites exhibited improved thermal properties, with the glass transition temperature (T_g) being shifted from 30 °C for unfilled CEOS to 54 °C (2 wt.% HP14) and 73 °C (2 wt.% OS1) for filled CEOS. Additionally, TGA analysis showed increased thermal stability of samples filled with nanoparticles. An attractive interaction between boehmite and CEOS matrix influenced the curing. Real-time infrared spectroscopy (RT-IR) experiments demonstrated that the epoxide conversion rate of nanocomposites was slightly increased compared to neat resin. The beneficial role of the BA can be explained by the participation of hydroxyl groups at the particle surface in photopolymerization processes and by the complementary contribution of p-toluenesulfonic acid surface modifier and water molecules introduced into the system with nanoparticles. Full article

A cationic photo-curable cycloaliphatic epoxy resin has been investigated as reactive monomer in blue light crosslinking process. We have demonstrated that camphorquinone is able to abstract labile hydrogen from the epoxy monomer, giving rise to the formation of carbon-centered radicals that are oxidized by the onium salt; a complete epoxy group conversion was reached after 50 s of irradiation. The presence of water up to 1 wt% was tolerated without any important detrimental effect on the kinetics of light-curing. The presence of the inorganic filler up to 65 wt% did not significantly influence the curing process. Full article