Additive manufacturing technology has significantly impacted contemporary industries due to its ability to generate intricate computer-designed geometries. However, 3D-printed polymer parts often possess limited application potential, primarily because of their weak mechanical attributes. To overcome this drawback, this study formulates liquid crystal/photocurable resins suitable for the stereolithography technique by integrating 4’-pentyl-4-cyanobiphenyl with a photosensitive acrylic resin. This study demonstrates that stereolithography facilitates the precise modulation of the existing liquid crystal morphology within the resin. Furthermore, the orientation of the liquid crystal governs the oriented polymerization of monomers or prepolymers bearing acrylate groups. The products of this 3D printing approach manifest anisotropic behavior. Remarkably, when utilizing liquid crystal/photocurable resins, the resulting 3D-printed objects are approximately twice as robust as those created using commercial resins in terms of their tensile, flexural, and impact properties. This pioneering approach holds promise for realizing autonomously designed structures that remain elusive with present additive manufacturing techniques.

Photosensitive resins used in three-dimensional (3D) printing are characterized by high forming precision and fast processing speed; however, they often possess poor mechanical properties and heat resistance. In this study, we report a photocurable bismaleimide ink with excellent comprehensive performance for stereolithography (SLA) 3D printing. First, the main chain of bismaleimide with an amino group (BDM) was synthesized, and then, the glycidyl methacrylate was grafted to the amino group to obtain the bismaleimide oligomer with an unsaturated double bond. The oligomers were combined with reaction diluents and photo-initiators to form photocurable inks that can be used for SLA 3D printing. The viscosity and curing behavior of the inks were studied, and the mechanical properties and heat resistance were tested. The tensile strength of 3D-printed samples based on BDM inks could reach 72.6 MPa (166% of that of commercial inks), glass transition temperature could reach 155 °C (205% of that of commercial inks), and energy storage modulus was 3625 MPa at 35 °C (327% of that of commercial inks). The maximum values of T_-5%, T_-50%, and T_max of the 3D samples printed by BDM inks reached 351.5, 449.6, and 451.9 °C, respectively. These photocured BDM inks can be used to produce complex structural components and models with excellent mechanical and thermal properties, such as car parts, building models, and pipes.

The terpolymerization of carbon dioxide (CO₂), propylene oxide (PO), and cyclohexene oxide (CHO) were performed by both random polymerization and block polymerization to synthesize the random poly (propylene cyclohexene carbonate) (PPCHC), di-block polymers of poly (propylene carbonate–cyclohexyl carbonate) (PPC-PCHC), and tri-block polymers of poly (cyclohexyl carbonate–propylene carbonate–cyclohexyl carbonate) (PCHC-PPC-PCHC). The kinetics of the thermal degradation of the terpolymers was investigated by the multiple heating rate method (Kissinger-Akahira-Sunose (KAS) method), the single heating rate method (Coats-Redfern method), and the Isoconversional kinetic analysis method proposed by Vyazovkin with the data from thermogravimetric analysis under dynamic conditions. The values of ln k vs. T⁻¹ for the thermal decomposition of four polymers demonstrate the thermal stability of PPC and PPC-PCHC are poorer than PPCHC and PCHC-PPC-PCHC. In addition, for PPCHC and PCHC-PPC-PCHC, there is an intersection between the two rate constant lines, which means that, for thermal stability of PPCHC, it is more stable than PCHC-PPC-PCHC at the temperature less than 309 °C and less stable when the decomposed temperature is more than 309 °C. Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and thermogravimetric analysis/infrared spectrometry (TG/FTIR) techniques were applied to investigate the thermal degradation behavior of the polymers. The results showed that unzipping was the main degradation mechanism of all polymers so the final pyrolysates were cyclic propylene carbonate and cyclic cyclohexene carbonate. For the block copolymers, the main chain scission reaction first occurs at PC-PC linkages initiating an unzipping reaction of PPC chain and then, at CHC–CHC linkages, initiating an unzipping reaction of the PCHC chain. That is why the T_−5% of di-block and tri-block polymers were not much higher than that of PPC while two maximum decomposition temperatures were observed for both the block copolymer and the second one were much higher than that of PPC. For PPCHC, the random arranged bulky cyclohexane groups in the polymer chain can effectively suppress the backbiting process and retard the unzipping reaction. Thus, it exhibited much higher T_−5% than that of PPC and block copolymers.

To mitigate the interlayer defects and weak interfacial adhesion inherent in FFF-printed parts, thereby facilitating subsequent supercritical foaming applications, a microwave-assisted interlayer healing strategy is developed for FFF-printed, supercritical CO₂-foamed thermoplastic polyurethane (TPU) by incorporating aminated helical multi-walled carbon nanotubes (AS-MWCNTs). Owing to their unique helical morphology, AS-MWCNTs exhibit enhanced microwave absorption and localized heating capability, enabling selective thermal activation at interlayer regions within the foamed architecture. Microwave irradiation induces localized softening of the TPU matrix and promotes polymer chain mobility and interdiffusion across layer interfaces, while preserving the cellular morphology and bulk foamed structure. By optimizing AS-MWCNT loading, substantial improvements in interlayer bonding strength, energy absorption, and overall mechanical performance are achieved. This work provides an effective strategy to restore interlayer integrity in supercritical CO₂-foamed, additive manufactured elastomers and offers insights into the design of microwave-responsive, self-healing cellular materials.