Biobased Imine Vitrimers Obtained by Photo and Thermal Curing Procedures-Promising Materials for 3D Printing.

Imine-based vitrimers were prepared from synthesized diimine-dimethacrylate monomer derived from biobased vanillin. First, a methacrylate derivative starting from vanillin was synthesized. The diimine derivative was synthesized by condensation of the aldehyde groups from two vanillin methacrylate units with the amine groups of hexamethylenediamine (HMDA). The synthesized product was used in formulations containing ethylene glycol phenyl ether methacrylate (EGPMA) as a reactive diluent for the customization of final material properties and cured by exposure to ultraviolet (UV)-light using suitable radical photoinitiators or else with temperature using a radical thermal initiator. Materials with glass transition temperatures (Tgs) ranging from 70 to 90 °C were prepared, showing good thermal stability and mechanical and thermomechanical properties. The evaluation of their vitrimeric characteristics revealed that all materials achieved a stress-relaxation factor (σ = 0.37σ0) in less than 130 s at 160 °C, with photocured materials exhibiting faster relaxation rates. The catalytic effect of phosphine oxide groups in imine metathesis has also been evidenced. All prepared materials could be mechanically recycled and completely solubilized in a two-step degradation process, putting evidence of their potential use for carbon fiber-reinforced composites (CFRCs). In addition, they demonstrated promising self-repairing abilities. Finally, as a proof of concept, it was established that these formulations could be effectively processed using a Digital Light Processing three-dimensional (3D) Printer (DLP), resulting in the fabrication of complex shapes with high resolution.

Optimization and Testing of Hybrid 3D Printing Vitrimer Resins.

The quality of photocure-based 3D printing greatly depends on the properties of the photoresin. There are still many challenges to be overcome at the material level before such additive manufacturing methods dominate the manufacturing industry. To contribute to this exciting re-search, an acrylate-epoxy hybrid and vitrimeric photoresin was studied to reveal the formulation parameters that could be leveraged to obtain improved processability, mechanical performance, and repairability/reprocessability. As the network becomes more lightly or densely crosslinked as a result of changing monomer compositions, or as its components are compatibilized to different extents by varying the types and loadings of the coupling agents, its thermomechanical, tensile, and vitrimeric behaviors are impacted. Using a particular formulation with a high concentration of dynamic ß-hydroxyester linkages, samples are 3D printed and tested for repair and recyclability. When processed at sufficiently high temperatures, transesterification reactions are triggered, allowing for the full recovery of the tensile properties of the repaired or recycled materials, despite their inherently crosslinked structure.

Cost-Effectively 3D-Printed Rigid and Versatile Interpenetrating Polymer Networks.

Versatile acrylate-epoxy hybrid formulations are becoming widespread in photo/thermal dual-processing scenarios, especially in 3D printing applications. Usually, parts are printed in a stereolithography or digital light processing (DLP) 3D printer, after which a thermal treatment would bestow the final material with superior mechanical properties. We report the successful formulation of such a hybrid system, consisting of a commercial 3D printing acrylate resin modified by an epoxy-anhydride mixture. In the final polymeric network, we observed segregation of an epoxy-rich phase as nano-domains, similar to what was observed in a previous work. However, in the current work, we show the effectiveness of a coupling agent added to the formulation to mitigate this segregation for when such phase separation is undesired. The hybrid materials showed significant improvement of Young's modulus over the neat acrylate. Once the flexible, partially-cured material was printed with a minimal number of layers, it could be molded into a complex form and thermally cured. Temporary shapes were readily programmable on this final material, with easy shape recovery under mild temperatures. Inspired by repairable 3D printed materials described recently, we manufactured a large object by printing its two halves, and then joined them covalently at the thermal cure stage with an apparently seamless union.

The Use of Click-Type Reactions in the Preparation of Thermosets.

Click chemistry has emerged as an effective polymerization method to obtain thermosets with enhanced properties for advanced applications. In this article, commonly used click reactions have been reviewed, highlighting their advantages in obtaining homogeneous polymer networks. The basic concepts necessary to understand network formation via click reactions, together with their main characteristics, are explained comprehensively. Some of the advanced applications of thermosets obtained by this methodology are also reviewed.

Enhancement of 3D-Printable Materials by Dual-Curing Procedures.

Dual-curing thermosetting systems are recently being developed as an alternative to conventional curing systems due to their processing flexibility and the possibility of enhancing the properties of cured parts in single- or multi-stage processing scenarios. Most dual-curing systems currently employed in three-dimensional (3D) printing technologies are aimed at improving the quality and properties of the printed parts. However, further benefit can be obtained from control in the curing sequence, making it possible to obtain partially reacted 3D-printed parts with tailored structure and properties, and to complete the reaction by activation of a second polymerization reaction in a subsequent processing stage. This paves the way for a range of novel applications based on the controlled reactivity and functionality of this intermediate material and the final consolidation of the 3D-printed part after this second processing stage. In this review, different strategies and the latest developments based on the concept of dual-curing are analyzed, with a focus on the enhanced functionality and emerging applications of the processed materials.

Synthesis and Thermophysical Characterization of Fatty Amides for Thermal Energy Storage.

Nine monoamides were synthesized from carboxylic acids (C8-C18) and crude glycerol. The final monoamides were the result of a rearrangement of the acyl chain during the final hydrogenation process. The purity of the final compounds was determined by spectroscopic and mass spectrometry (MS) techniques. The thermophysical properties of solid monoamides were investigated to determine their capability to act as phase change materials (PCM) in thermal energy storage. Thermophysical properties were determined with a differential scanning calorimeter (DSC). The melting temperatures of the analyzed material ranged from 62.2 °C to 116.4 °C. The analyzed enthalpy of these monoamides ranged from 25.8 kJ/kg to 149.7 kJ/kg. Enthalpy values are analyzed considering the carbon chain and the formation of hydrogen bonds.

Acetoacetate Based Thermosets Prepared by Dual-Michael Addition Reactions.

A novel set of dual-curable multiacetoacetate-multiacrylate-divinyl sulfone ternary materials with versatile and manipulable properties are presented. In contrast to common dual-curing systems, the first stage polymer herein consists of a densely crosslinked, high Tg network as a result of base-catalyzed multiacetoacetate-divinyl sulfone Michael addition. A more flexible secondary network forms after base-catalyzed Michael addition of remaining multiacetoacetate to multiacrylate. Curing is truly sequential as the rates of the two Michael additions are significantly different. Curing kinetics were analyzed using differential scanning calorimetry (DSC) and Fourier-transform infrared (FTIR). The materials at each curing stage were characterized using dynamic mechanical analysis (DMA) and SEM. Although some phase separation was observed in certain formulations, the incompatibilities were minimized when the molar percentage of the acetoacetate-divinyl sulfone polymer network was above 75%. Furthermore, the environmental scanning electron microscopy (ESEM) images of these materials show that the more flexible acetoacetate-acrylate phase is dispersed in the form of polymeric spheres within the rigid acetoacetate-divinyl sulfone matrix. This unique dual microstructure can potentially render these materials highly resilient in applications requiring densely crosslinked polymer architectures with enhanced toughness.

Rheological and Mechanical Characterization of Dual-Curing Thiol-Acrylate-Epoxy Thermosets for Advanced Applications.

Mechanical and rheological properties of novel dual-curing system based on sequential thiol-acrylate and thiol-epoxy reactions are studied with the aim of addressing the obtained materials to suitable advanced applications. The crosslinking process is studied by rheological analysis in order to determine conversion at gelation and the critical ratio. These parameters are used to discuss the intermediate material structure for each acrylate proportion and their possible application in the context of dual-curing and multi-step processing scenarios. Results from dynamo-mechanical analysis and mechanical testing demonstrate the high versatility materials under investigation and revealed a wide range of achievable final properties by simply varying the proportion between acrylate and thiol group. The intermediate stability between curing stages has been analysed in terms of their thermal and mechanical properties, showing that these materials can be stored at different temperatures for a relevant amount of time without experiencing significant effects on the processability. Experimental tests were made to visually demonstrate the versatility of these materials. Qualitative tests on the obtained materials confirm the possibility of obtaining complex shaped samples and highlight interesting shape-memory and adhesive properties.

Thermal Conductive Composites Prepared by Addition of Several Ceramic Fillers to Thermally Cationic Curing Cycloaliphatic Epoxy Resins.

Novel composite coatings prepared from 3,4-epoxy cyclohexylmethyl 3,4-epoxycyclohexane carboxylate (ECC) and different ceramic fillers have been prepared to improve the thermal dissipation of electronic devices. As latent cationic initiator, a benzylanilinium salt with triethanolamine has been used, which leads to a polyether matrix. Different proportions of Al2O3, AlN and SiC as fillers were added to the reactive formulation. The effect of the fillers selected and their proportions on the evolution of the curing was studied by calorimetry and rheometry. The thermal conductivity, thermal stability, thermal expansion coefficient and thermomechanical and mechanical properties of the composites were evaluated. An improvement of 820% in thermal conductivity in reference to the neat material was reached with a 75 wt % of AlN, whereas glass transition temperatures higher than 200 °C were determined in all the composites.

State of the Art in Dual-Curing Acrylate Systems.

Acrylate chemistry has found widespread use in dual-curing systems over the years. Acrylates are cheap, easily handled and versatile monomers that can undergo facile chain-wise or step-wise polymerization reactions that are mostly of the "click" nature. Their dual-curing processes yield two distinct and temporally stable sets of material properties at each curing stage, thereby allowing process flexibility. The review begins with an introduction to acrylate-based click chemistries behind dual-curing systems and relevant reaction mechanisms. It then provides an overview of reaction combinations that can be encountered in these systems. It finishes with a survey of recent and breakthrough research in acrylate dual-curing materials for shape memory polymers, optical materials, photolithography, protective coatings, structured surface topologies, and holographic materials.

Epoxy-Based Shape-Memory Actuators Obtained via Dual-Curing of Off-Stoichiometric "Thiol⁻Epoxy" Mixtures.

In this work, epoxy-based shape-memory actuators have been developed by taking advantage of the sequential dual-curing of off-stoichiometric "thiol⁻epoxy" systems. Bent-shaped designs for flexural actuation were obtained thanks to the easy processing of these materials in the intermediate stage (after the first curing process), and successfully fixed through the second curing process. The samples were programmed into a flat temporary-shape and the recovery-process was analyzed in unconstrained, partially-constrained and fully-constrained conditions using a dynamic mechanical analyzer (DMA). Different "thiol⁻epoxy" systems and off-stoichiometric ratios were used to analyze the effect of the network structure on the actuation performance. The results evidenced the possibility to take advantage of the flexural recovery as a potential actuator, the operation of which can be modulated by changing the network structure and properties of the material. Under unconstrained-recovery conditions, faster and narrower recovery-processes (an average speed up to 80%/min) are attained by using materials with homogeneous network structure, while in partially- or fully-constrained conditions, a higher crosslinking density and the presence of crosslinks of higher functionality lead to a higher amount of energy released during the recovery-process, thus, increasing the work or the force released. Finally, an easy approach for the prediction of the work released by the shape-memory actuator has been proposed.

Simultaneous monitoring of curing shrinkage and degree of cure of thermosets by attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopy.

We present a novel methodology to simultaneously monitor of the degree of cure and curing shrinkage of thermosetting formulations. This methodology is based on the observation of changes in the infrared absorption of reactive functional groups and the groups used as a standard reference for normalization. While the optical path length is exact and controlled in transmission infrared spectroscopy, in attenuated total reflection Fourier transform infrared (ATR FT-IR), the exact determination of volume changes requires the measurement of the refractive indices of the studied system throughout the curing process or at least an indirect parallel measurement of this property. The methodology presented here allows one to achieve quantitative measurements of the degree of cure and shrinkage for thermosets using in situ ATR FT-IR spectroscopy.

Laccase-assisted formation of bioactive chitosan/gelatin hydrogel stabilized with plant polyphenols.

Laccase-assisted simultaneous cross-linking and functionalization of chitosan/gelatin blends with phenolic compounds from Hamamelis virginiana was investigated for the development of bioactive hydrogel dressings. The potential of these hydrogels for chronic wound treatment was evaluated in vitro, assessing their antibacterial and inhibitory effect on myeloperoxidase and collagenase. Rheological studies revealed that the mechanical properties of the hydrogels were a function of the enzymatic reaction time. Stable hydrogels and resistant to lysozyme degradation were achieved after 2 h laccase reaction. The inhibitory capacity of the hydrogel for myeloperoxidase and collagenase was 32% and 79% respectively after 24 h incubation. Collagenase activity was additionally suppressed by adsorption (20%) of the enzyme onto the hydrogel. Therefore, the bioactive properties of the hydrogels were due to the effect of both released phenolic compounds and the permanently functionalized platform itself. The hydrogels showed antibacterial activity against Pseudomonas aeruginosa and Staphylococcus aureus.