Magnetic-Oriented Nickel Particles and Nickel-Coated Carbon Nanotubes: An Efficient Tool for Enhancing Thermal Conductivity of PDMS Composites

In this study, PDMS composites are thermally cured with nickel particles and nickel-coated carbon nanotubes as fillers. Both fillers are oriented with the aim to increase the thermal conductivity of the silicone polymer network, due to the formation of a continuous thermal path. Scanning electron microscopy (SEM) gives a picture of the polymer network's morphology, proving the effective alignment of the nickel particles. Rheology and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) studies confirm the full curing of the silicon network and no influence in the curing kinetics of the type and content of fillers and their orientation. Dynamic mechanical thermal analysis (DMTA) and tensile analysis show instead different thermo-mechanical behavior of the polymer network due to the presence of different fillers, different fillers percentage, and orientation. Finally, the thermal transmittance coefficient (k) is studied by means of hot disk analysis, revealing the increment of almost 200% due to magnetic filler orientation

Hot-Lithography SLA-3D Printing of Epoxy Resin

The hot-lithography stereolithography 3D printing technology is used to print epoxy resins with high reactivity in order to achieve 3D printed structures. Different hydroxyl containing compounds are investigated as chain transfer agents and the viscoelastic properties of UV-cured materials are fully characterized. The most promising formulations are studied at a high temperature, the 3D printing process parameters are defined and the printed object is fully characterized. By combining the suitable precursor materials in the photocurable formulation with the advanced hot-lithography process, it is possible to produce 3D printed structures that are characterized by outstanding thermomechanical properties and good printability precision

Microwave-assisted methacrylation of chitosan for 3D printable hydrogels in tissue engineering

Light processable natural polymers are highly attractive for 3D printing of biomedical hydrogels with defined geometries and sizes. However, functionalization with photo-curable groups, such as methacrylate or acrylate groups, is required. Here, we investigated a microwave-assisted process for methacrylation of chitosan to replace conventional methacrylation processes that can be time consuming and tedious. The microwave-assisted methacrylation reaction was optimized by varying the synthesis parameters such as the molar ratio of chitosan to the methacrylic agent, the launch and reaction times and process temperature. The optimized process was fast and efficient and allowed tuning of the degree of substitution and thereby the final hydrogel properties. The successful methacrylation and degree of substitution were verified by H-1 NMR and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). The influence of the degree of methacrylation on photo-rheology, mechanical stiffness, swelling degree and gel content was evaluated. Furthermore, favourable 3D printability, enzymatic degradability, biocompatibility, cell migration and proliferation were demonstrated giving promise for further applications in tissue engineering

DLP 3D printing meets lignocellulosic biopolymers: Carboxymethyl cellulose inks for 3D biocompatible hydrogels

The development of new bio-based inks is a stringent request for the expansion of additive manufacturing towards the development of 3D-printed biocompatible hydrogels. Herein, methacrylated carboxymethyl cellulose (M-CMC) is investigated as a bio-based photocurable ink for digital light processing (DLP) 3D printing. CMC is chemically modified using methacrylic anhydride. Successful methacrylation is confirmed by 1H NMR and FTIR spectroscopy. Aqueous formulations based on M-CMC/lithium phenyl-2,4,6-trimethylbenzoylphosphinate (LAP) photoinitiator and M-CMC/Dulbecco's Modified Eagle Medium (DMEM)/LAP show high photoreactivity upon UV irradiation as confirmed by photorheology and FTIR. The same formulations can be easily 3D-printed through a DLP apparatus to produce 3D shaped hydrogels with excellent swelling ability and mechanical properties. Envisaging the application of the hydrogels in the biomedical field, cytotoxicity is also evaluated. The light-induced printing of cellulose-based hydrogels represents a significant step forward in the production of new DLP inks suitable for biomedical applications

DLP 4D-Printing of Remotely, Modularly, and Selectively Controllable Shape Memory Polymer Nanocomposites Embedding Carbon Nanotubes

AbstractAn in‐depth investigation on novel electro‐activated shape memory polymer composites (SMPCs) for digital light processing 3D‐Printing, consisting of a poly(ethylene glycol) diacrylate/poly(hydroxyethyl methacrylate) matrix embedding multi‐walled carbon nanotubes (CNTs), is reported here. The composition of the photocurable (meth)acrylate system is finely tuned to tailor the thermomechanical properties of the matrix, whereas the effect of CNTs on the photoreactivity and rheological properties of the formulations is investigated to assess the printability. Electrical measurements confirmed that the incorporation of CNT into the polymeric matrix enables the electrical conductivity and thus the possibility to remotely heat the nanocomposite using the Joule effect. The feasibility to drive a shape memory cycle via Joule heating is proved, given that the high shape fixity (Rf) and shape recovery (Rr) ratios achieved (Rf ≈ 100%, Rr > 95%) confirmed the significant electrically‐triggered responsiveness of such CNT/SMPCs. Finally, it is shown how to activate a modular and selective electro‐activated shape recovery, which may ultimately envisage the 4D‐Printing of remotely and selectively controllable smart devices

Dual-curable stereolithography resins for superior thermomechanical properties

Stereolithography (SL) stands out as a relatively fast additive manufacturing method to produce thermoset components with high resolutions. The majority of SL resins consist of acrylate monomers which result in materials with cur-ing-induced shrinkage problems and this, in addition to the incomplete and non-uniform conversions reached in the SL process, results in poor mechanical properties. To address this issue, a dual-curing formulation was developed by mixing an epoxy monomer into a commercial multi-acrylate SL resin: the first curing stage is acrylate free-radical photopolymerization at ambient temperature, and the second curing stage is cationic epoxy homopolymerization at higher temperatures. The fully dual-cured materials are macroscopically homogeneous, with nanoscale domains observed by Atomic Force Mi-croscopy (AFM), and with unimodal tan delta peaks observed in Dynamic Mechanical Analysis (DMA). The uncured material was storage stable at ambient conditions for at least 9 weeks since the epoxy part was virtually unreactive at these temper-atures. With the dual-cured materials, a nearly 10-fold increase in Young’s modulus was achieved over the neat acrylate resin. At the thermal curing stage, the presence of diperoxyketal thermal radical initiator to the liquid formulation facilitated the polymerization of unreacted acrylates that remained from the SL process simultaneously with epoxy homopolymerization and helped the material attain improved properties