For the first time, the synergy of shape memory polymer (SMP) blending, 4D printing, and cold programming (CP) are investigated for improving the functionality of the shape memory effect (SME), increasing medical applications of porous structures, direct programming, and removing current limitations. Porous PLA-TPU structures with different printing patterns and applied deformation were CPed under constrained and non-constrained compression modes at room temperature and were recovered in the rubbery phase. The shape fixity and shape recovery ratios were calculated and the cross-section morphology was examined with scanning electron microscopy (SEM). The shape fixity values were in the range of 39.75%–71.27%, while almost complete shape recovery ratios (100%) were observed for all porous samples. Low shape fixity ratios can be justified due to the existence of two steps of spring-back and structure relaxation after unloading in cold programming, resulting from elastic and viscoelastic behavior. The glass transition temperature of the PLA-TPU blend was 69 °C and shifted to raw materials, indicating the possibility of some interaction between the two components. SEM images showed the uniform distribution of TPU particles and matrix-droplet morphology in the PLA-TPU blend. After printing, TPU droplets were stretched and the sea-island morphology was observed in some segments.

This study introduces novel PETG–ABS–Fe₃O₄ nanocomposites that offer impressive 3D- and 4D-printing capabilities. These nanocomposites can be remotely stimulated through the application of a temperature-induced magnetic field. A direct granule-based FDM printer equipped with a pneumatic system to control the output melt flow is utilized to print the composites. This addresses challenges associated with using a high weight percentage of nanoparticles and the lack of control over geometry when producing precise and continuous filaments. SEM results showed that the interface of the matrix was smooth and uniform, and the increase in nanoparticles weakened the interface of the printed layers. The ultimate tensile strength (UTS) increased from 25.98 MPa for the pure PETG–ABS sample to 26.3 MPa and 27.05 MPa for the 10% and 15% Fe₃O₄ nanocomposites, respectively. This increase in tensile strength was accompanied by a decrease in elongation from 15.15% to 13.94% and 12.78%. The results of the shape-memory performance reveal that adding iron oxide not only enables indirect and remote recovery but also improves the shape-memory effect. Improving heat transfer and strengthening the elastic component can increase the rate and amount of shape recovery. Nanocomposites containing 20% iron oxide demonstrate superior shape-memory performance when subjected to direct heat stimulation and a magnetic field, despite exhibiting low print quality and poor tensile strength. Smart nanocomposites with magnetic remote-control capabilities provide opportunities for 4D printing in diverse industries, particularly in medicine, where rapid speed and remote control are essential for minimally invasive procedures.

In this study, for the first time, post-heat treatment was applied to improve the stress recovery of short carbon fiber reinforced PETG (SCFRPETG). PETG and SCFRPETG composite were printed under optimal conditions, and constrained and free shape memory cycles were applied under compression and three-point bending loadings to assess shape and stress recovery. The results of the free shape memory test for both vertical and horizontal patterns showed that PETG composite also has a higher shape memory effect (SME) compared to PETG. The SME was significantly improved by performing heat treatment. The stress recovery values for pure PETG, reinforced PETG before and after annealing are 2.48 MPa, 3.04 MPa and 3.18 MPa, respectively. It showed that the addition of 1.5% carbon fiber increases the stress recovery by 22%. The increasing trend reaches 28% by performing post-heat treatment. Additionally, altering the printing pattern affects the programming and stress recovery values. For the SCFRPETG composite samples before and after annealing, changing the printing pattern from horizontal to vertical, resulted in a 16% and 7% increase in recovery stress, respectively. SEM results confirm that the annealing process removes the layered structure, micro-holes caused by shrinkage and 4D printing mechanism. Using the controlled heat treatment method can be a practical solution to solve the problem of adhesion and reduce the anisotropy of FDM 3D printed layers.

The main novelty of this paper is the use of poly-ethylene terephthalate glycol (PETG) as a new shape memory polymer with excellent shape memory effect (SME) and printability. In addition, for the first time, the effect of programming temperature on PETG 4D printed samples has been studied. The amorphous nature of the PETG necessitates that molecular entanglements function as net points, which makes the role of programming temperature critical. SME comprehensively was conducted under compression loading for three programming conditions as well as various pre-strains. Significant results were obtained that summarized the gross differences exhibiting that the hot, cold, and warm programmed samples had the highest shape fixity, shape recovery, and stress recovery, respectively. The recovery and fixity ratios fell and rose, respectively, as the programming temperature increased. This effect intensified in hot programmed samples as the applied strain (loading time) expanded. So, the recovery ratio dropped from 68% to 50% by raising the pre-strain from 20% to 80%. The maximum stress recovery was 16 MPa, suggesting the fantastic benefit of warm programming conditions in PETG 4D printed parts. The locking mechanism (recovery force storage) for cold and hot programming is quite different. The dominant mechanism in cold programming is increasing internal energy by potential energy level enhancement. Contrary to this, in hot programming, the entropy reduction applies to the majority of the molecular segments, playing this role. By cooling, the state of the material changes from rubbery to glassy, and with this phase change, the oriented conformation of the deformed polymer chains is maintained under deformation. The results of this research can be used for various applications that require high shape fixity, recovery, or stress recovery.

In this study, a new strategy and design for achieving a shape memory effect (SME) and 4D printed two-layer composite structures is unveiled, thanks to fused deposition modeling (FDM) biomaterial printing of commercial filaments, which do not have an SME. We used ABS and PCL as two well-known thermoplastics, and TPU as elastomer filaments that were printed in a two-layer structure. The thermoplastic layer plays the role of constraint for the elastomeric layer. A rubber-to-glass transition of the thermoplastic layer acts as a switching phenomenon that provides the capability of stabilizing the temporary shape, as well as storing the deformation stress for the subsequent recovery of the permanent shape by phase changing the thermoplastic layer in the opposite direction. The results show that ABS–TPU had fixity and recovery ratios above 90%. The PCL–TPU composite structure also demonstrated complete recovery, but its fixity was 77.42%. The difference in the SME of the two composite structures is related to the transition for each thermoplastic and programming temperature. Additionally, in the early cycles, the shape-memory performance decreased, and in the fourth and fifth cycles, it almost stabilized. The scanning electron microscopy (SEM) photographs illustrated superior interfacial bonding and part integrity in the case of multi-material 3D printing.