4D printing and optimization of biocompatible poly lactic acid/poly methyl methacrylate blends for enhanced shape memory and mechanical properties

This study introduces a novel approach to 4D printing of biocompatible Poly lactic acid (PLA)/poly methyl methacrylate (PMMA) blends using Artificial Neural Network (ANN) and Response Surface Methodology (RSM). The goal is to optimize PMMA content, nozzle temperature, raster angle, and printing speed to enhance shape memory properties and mechanical strength. The materials, PLA and PMMA, are melt-blended and 4D printed using a pellet-based 3D printer. Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Thermal Analysis (DMTA) assess the thermal behavior and compatibility of the blends. The ANN model demonstrates superior prediction accuracy and generalization capability compared to the RSM model. Experimental results show a shape recovery ratio of 100% and an ultimate tensile strength of 65.2 MPa, significantly higher than pure PLA. A bio-screw, 4D printed with optimized parameters, demonstrates excellent mechanical properties and shape memory behavior, suitable for biomedical applications such as orthopaedics and dental implants. This research presents an innovative method for 4D printing PLA/PMMA blends, highlighting their potential in creating advanced, high-performance biocompatible materials for medical use

3D and 4D printing of PETG–ABS–Fe3O4 nanocomposites with supreme remotely driven magneto-thermal shape-memory performance

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

Poly(ethylene terephthalate) glycol/carbon black composites for 4D printing

This research introduces PETG-CB (poly(ethylene terephthalate) glycol modified with carbon black) composites, a new class of shape memory polymers 4D printed using the Fused Deposition Modeling (FDM) method. Nanocomposites with varying concentrations of CB (0.5 %, 1 %, and 3 % by weight) are developed to enhance the functional performance of PETG in 4D printing applications. Comprehensive characterization at the micro- and macro-scale, including dynamic thermal mechanical analysis (DMTA), scanning electron microscopy (SEM), and mechanical testing, is employed to assess the viscoelastic behavior, microstructural integrity, and mechanical strength under thermal stimulation. Experimental results reveal that CB addition significantly alters the glass transition temperature and improves mechanical properties, with the 1 % CB composite demonstrating optimal tensile strength and enhanced shape memory effects. SEM analysis confirms a uniform distribution of CB particles, contributing to the improved mechanical properties and printability of the nanocomposites. The shape memory tests show excellent recovery rates above 97 %, with faster recovery observed in composites with higher CB content. These findings highlight the potential of PETG-CB composites in applications requiring rapid response and high mechanical performance, making them promising materials for future advancements in the 4D printing technology

Effects of TPU on the mechanical properties, fracture toughness, morphology, and thermal analysis of 3D‐printed ABS‐TPU blends by FDM

In this paper, blends of ABS-TPU with two different weight percentages of TPU were prepared using fused deposition modeling technology. The effect of adding TPU on the fracture toughness of ABS and mechanical properties was comprehensively studied. Tensile, compression, fracture toughness, and shear tests were conducted on the 3D-printed samples. Thermal and microstructural analyses were performed using dynamic mechanical thermal analysis (DMTA), and scanning electron microscope (SEM). The DMTA results showed that adding TPU decreased the storage modulus and the glass transition temperature of ABS, as well as its peak intensity. The mechanical test results showed that adding TPU decreased the strength but increased the formability and elongation of the samples. Fracture tests showed that the addition of TPU decreased the maximum force needed for a crack to initiate. The force required for crack initiation decreased from 568.4 N for neat ABS to 335.3 N for ABS80 and 123.2 N for ABS60. The ABS60 blend exhibited the highest strength against crack growth, indicating that TPU can change the behavior of ABS from brittle to ductile. Shear test results and SEM images also showed good adhesion strength between the printed samples for all three specimens, indicating their good printability. Adding TPU resulted in a reduction in the size and number of voids and holes between the printed layers

4D printing-encapsulated polycaprolactone–thermoplastic polyurethane with high shape memory performances

There are a few shape memory polymers (SMPs) like polylactic acid (PLA) and polyurethane (PU) that are 4D printable, and other SMPs must be synthesized with a complicated chemical lab effort. Herein, considering dual-material extrusion printing and microscopic mechanism behind shape memory effect (SME), bilayer-encapsulated polycaprolactone (PCL)–thermoplastic polyurethane (TPU) shape memory composite structures are 4D printed for the first time. The SME performance is investigated by assessing fixity, shape recovery, stress recovery, and stress relaxation under bending and compression loading modes. PCL, TPU, and melting temperature of PCL play the role of switching phase, net point, and transition temperature, respectively. Due to the destruction and dripping of molten PCL in contact with water, PCL is encapsulated by TPU. Encapsulation successfully solves the challenge of bonding/interface between printed layers, and the results show that the SME performance of the encapsulated structures is higher than bilayer PCL–TPU one's. Experiments reveal that maximum stress recovery in 4D-printed composites remains constant over time. This is a great achievement compared to the previous extrusion-based SMP structures that have great weakness in stress relaxation due to weak and low crystalline fractions and the unraveling of molecular entanglements in semicrystalline and amorphous thermoplastic SMPs, respectively

Development of pure poly vinyl chloride (PVC) with excellent 3D printability and macro‐ and micro‐structural properties

Unmodified polyvinyl chloride (PVC) has low thermal stability and high hardness. Therefore, using plasticizers as well as thermal stabilizers is inevitable, while it causes serious environmental and health issues. In this work, for the first time, pure food-grade PVC with potential biomedical applications is processed and 3D printed. Samples are successfully 3D printed using different printing parameters, including velocity, raster angle, nozzle diameter, and layer thickness, and their mechanical properties are investigated in compression, bending, and tension modes. Scanning electron microscopy is also used to evaluate the bonding and microstructure of the printed layers. Among the mentioned printing parameters, raster angle and printing velocity influence the mechanical properties significantly, whereas the layer thickness and nozzle diameter has a little effect. Images from scanning electron microscopy also reveal that printing velocity greatly affects the final part's quality regarding defective voids and rasters’ bonding. The maximum tensile strength of 88.55 MPa is achieved, which implies the superiority of 3D-printed PVC mechanical properties compared to other commercial filaments. This study opens an avenue to additively manufacture PVC that is the second most-consumed polymer with cost-effective and high-strength features

Influence of the liver vascular distribution on its overall mechanical behavior: A first approach to multiscale fluid-structure homogenization

Medical applications require the numerical models to be both precise and quickly computed. In the context of liver surgery, this study aims to develop a homogenized mechanical model of the liver accounting for both hepatic tissue properties and macroscopic level blood flow impact. For this, a fluid analysis is carried out to simulate the blood flow inside the liver vessels and extract the pressure on the liver vascularization walls. This pressure is then integrated through a homogenization study, based first on alternative Eshelby type approach, then through a Mori-Tanaka scheme to compute the equivalent material rigidity. Once the equivalent mechanical properties identified, they are integrated into the macroscopic liver model, allowing a light quickly computed model integrating the underlying physics relying on the blood flow mechanical impact

4D printing thermo-magneto-responsive PETG-Fe3O4 nanocomposites with enhanced shape memory effects

In this groundbreaking study, Polyethylene Terephthalate Glycol (PETG)-Fe3O4 nanocomposites were developed for 4D printing, incorporating iron oxide (Fe3O4) nanoparticles into PETG matrix. The research contribution lies in its innovative approach to enhancing the shape memory effect (SME) through thermo-magnetic responsiveness, positioning PETG-Fe3O4 as a revolutionary material in smart additive manufacturing. The composites were synthesized using a melt mixing method, followed by 3D printing into specimens for comprehensive evaluation through dynamic mechanical thermal analysis (DMTA), scanning electron microscopy (SEM), and uniaxial tensile tests. The findings revealed that the incorporation of Fe3O4 nanoparticles significantly boosts the composites’ storage modulus and glass transition temperature, indicative of improved stiffness and thermal properties. Notably, the 15 % Fe3O4 composite emerged as the optimal blend, exhibiting the highest tensile strength and a favourable balance between mechanical integrity and flexibility. A key result was the enhanced SME under both thermal and magnetic stimuli, with recovery efficiency and speed escalating with nanoparticle concentration. This advancement underscores the potential of PETG-Fe3O4 nanocomposites in fabricating smart structures capable of environmental adaptability, paving the way for impacts in biomedical, aerospace, and robotic devices. Through this work, a new paradigm in material functionality for 4D printing has been established, demonstrating the viability of magnetic nanoparticle integration for added smart capabilities

4D printing of polyvinyl chloride (PVC): a detailed analysis of microstructure, programming, and shape memory performance

In this research, polyvinyl chloride (PVC) with excellent shape-memory effects is 4D printed via fused deposition modeling (FDM) technology. An experimental procedure for successful 3D printing of lab-made filament from PVC granules is introduced. Macro- and microstructural features of 3D printed PVC are investigated by means of wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), and dynamic mechanical thermal analysis (DMTA) techniques. A promising shape-memory feature of PVC is hypothesized from the presence of small close imperfect thermodynamically stable crystallites as physical crosslinks, which are further reinforced by mesomorphs and possibly molecular entanglement. A detailed analysis of shape fixity and shape recovery performance of 3D printed PVC is carried out considering three programming scenarios of cold (Tg −45 °C), warm (Tg −15 °C), and hot (Tg +15 °C) and two load holding times of 0 s, and 600 s under three-point bending and compression modes. Extensive insightful discussions are presented, and in conclusion, shape-memory effects are promising, ranging from 83.24% to 100%. Due to the absence of similar results in the specialized literature, this paper is likely to fill a gap in the state-of-the-art shape-memory materials library for 4D printing, and provide pertinent results that are instrumental in the 3D printing of shape-memory PVC-based structures

A new strategy for achieving shape memory effects in 4D printed two-layer composite structures

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