Sustainable 4D printing of magneto-electroactive shape memory polymer composites

Shape memory polymers (SMPs) are evolving intensively in smart materials research. SMPs can undergo large deformations, hold a temporary shape and then recover their original shape upon exposure to a particular external stimulus. The emerging development of fibre reinforced shape memory polymer composites (SMPCs) has improved SMPs’ mechanical properties to be comparable to modern fibre reinforced composites. Moreover, the inclusion of nanoparticles has enhanced the diversity in activation mechanisms and improved structural properties and durability.
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\nToday, the SMPCs are generally viewed as promising substances for engineered applications that have raised intensive interest among the scientists and engineers. Interestingly, stimulation by light enables unique and advanced shape memory effects (SMEs) in SMPCs that can fulfill the sophisticated demands of engineering. The ability to vary the light wavelength, intensity, periodicity, polarization and the irradiated position on the SMP component enables wavelength selective, reversible, sequential and multiple SMEs. Furthermore, light travel long distances in a vacuum, can be focussed onto a certain area, is safe to humans and, can be a control signal carrier and most notably, can be sent through optical fibres to extremely inaccessible areas.
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\nIncorporation of metallic, carbon and organic based photothermal fillers into a SMP matrix is a convenient proven method to prepare light activated shape memory polymer composites (LASMPCs). These photothermal fillers convert electromagnetic radiation into thermal energy that triggers the SMP matrix. The current study comprehensively reviewed the performances, mechanisms, challenges and limitations of the existing LASMPC systems and associated optical technologies. Predominantly this research was intended to develop reinforced LASMPC systems and allied optical technologies applicable for large scale structural engineering applications.
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\nIn this study, styrene and bisphenol A epoxy based thermosets and polylactic acid (PLA) based thermoplastic SMPs were used as polymer matrix materials. Carbon fibre, glass fibre, multiwalled carbon nanotube (MWCNT) and rare earth organic complexes of Nd(TTA)3Phen and Yb(TTA)3Phen were used as reinforcement and photothermal fillers. The samples were produced by means of vacuum bagging, mould casting and 4D printing. Morphological investigations were conducted to identify the microstructure and manufacturability of the LASMPCs. The samples’ mechanical and physical properties were tested by standard test methods for polymer matrix composites. Dynamic mechanical analysis was carried out to determine the thermomechanical characteristics. The photothermal effect was investigated through thermal imaging and associated shape memory behaviours were studied through shape fixing and recovery experiments. A finite element analysis was performed with ABAQUS to simulate the photothermal heating behaviour.
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\nThe current study established a material development framework for LASMPC materials and presented apt manufacturing methods for structural and large scale engineering applications. Different modes of light diffusion such as scattered low intensity light, focussed laser beams and light delivery through fibre optics were proved for structural LASMPCs. Sequential and selective wavelength activation of structural LASMPCs are presented. The FEA simulation provided additional understanding on light exposed LASMPCs’ 3-dimensional heating behaviour. Embedding a D-shaped optical fibre in an LASMPC created a single unit smart actuator, which was remotely activated by light. It was proven that flexible radiation shields can reduce the unanticipated shape recovery of LASMPCs components and protect the LASMPCs from polymer degradation due to radiation.
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\nThe improvements to their structural properties and innovative remote activation methodologies have justified LASMPCs’ aptness for space engineering applications. This study has proven its successful completion by three selected case studies of space applications. An LASMPC solar panel array model was sequentially deployed in four recovery steps. In a vacuum, a space habitat structure model was compressed to a third of its volume and then recovered its original shape. A 4D printed boom structure model was tested, proving customized LASMPC structures for sophisticated space equipment fabrication. The deployable LASMPC structures can reduce the occupied room in spacecraft. The improvements to the structural properties of LASMPCs while keeping the SME, understanding on thermomechanical and photothermal behaviours, remote actuation through optical fibres, radiation shields and the insight to space applications are the most significant novel outcomes of this study. This thesis opens up windows of opportunity for the scientific and engineering communities to provide innovative solutions to realize the sophisticated large scale engineering demands in aerospace and space applications and beyond.

The existing 3D printing methods exhibit certain fabrication-dependent limitations for printing curved constructs that are relevant for many tissues. Four-dimensional (4D) printing is an emerging technology that is expected to revolutionize the field of tissue engineering and regenerative medicine (TERM). 4D printing is based on 3D printing, featuring the introduction of time as the fourth dimension, in which there is a transition from a 3D printed scaffold to a new, distinct, and stable state, upon the application of one or more stimuli. Here, we present an overview of the current developments of the 4D printing technology for TERM, with a focus on approaches to achieve temporal changes of the shape of the printed constructs that would enable biofabrication of highly complex structures. To this aim, the printing methods, types of stimuli, shape-shifting mechanisms, and cell-incorporation strategies are critically reviewed. Furthermore, the challenges of this very recent biofabrication technology as well as the future research directions are discussed. Our findings show that the most common printing methods so far are stereolithography (SLA) and extrusion bioprinting, followed by fused deposition modelling, while the shape-shifting mechanisms used for TERM applications are shape-memory and differential swelling for 4D printing and 4D bioprinting, respectively. For shape-memory mechanism, there is a high prevalence of synthetic materials, such as polylactic acid (PLA), poly(glycerol dodecanoate) acrylate (PGDA), or polyurethanes. On the other hand, different acrylate combinations of alginate, hyaluronan, or gelatin have been used for differential swelling-based 4D transformations. TERM applications include bone, vascular, and cardiac tissues as the main target of the 4D (bio)printing technology. The field has great potential for further development by considering the combination of multiple stimuli, the use of a wider range of 4D techniques, and the implementation of computational-assisted strategies.

4D printed and multi-stimulus responsive shape memory polymer nanocomposites developed on hydrogen bonding–metal-phenolic sacrificial network: Application for hazardous chemical operations soft robots

Hygromorphic smart structures are advantageous as passively actuated systems for generating movement, with applications ranging from weather-responsive architectural building skins to adaptive wearables and microrobotics. Four-dimensional (4D) printing is a valuable method for multiscale fabrication and physical programming of such structures. However, material limitations in terms of printability, responsiveness, and mechanical properties are major bottlenecks in achieving reliable and repeatable humidity-responsive actuation. We propose a codesign method for 4D printing hygromorphic structures through fused filament fabrication, incorporating parallel development of (1) biobased cellulose-filled filaments with varying stiffness and hygroresponsiveness, and (2) designed mesoscale structuring in printed elements. We first describe the design of a pallet of filaments produced by compounding cellulose powder in mass ratios of 0–30% within two matrix polymers with high and low stiffness. We then present the design, fabrication, and testing of a series of 4D-printed prototypes tuned to change shape, that is, open and close, in response to relative humidity (RH). The structures can fully transform in conditions of 35–90% RH, which corresponds to naturally occurring shifts in RH in daily and seasonal weather cycles. Furthermore, their motion is fast (within the range of minutes), fully reversible, and repeatable in numerous cycles. These results open new opportunities for the utilization of 4D printing and natural resources for the development of functional humidity-responsive smart structures.

Material characterization and precise finite element analysis of fiber reinforced thermoplastic composites for 4D printing

Four-dimensional (4D) printing technology, as a next-generation additive manufacturing method, enables printed objects to further change their shapes, functionalities, or properties upon exposure to external stimuli. The 4D printing of programmable and deformable materials such as thermo-responsive shape-memory polymers (trSMPs), which possess the ability to change shape by exposure to heat, has attracted particular interest in recent years. Three-dimensional objects based on SMPs have been proposed for various potential applications in different fields, including soft robotics, smart actuators, biomedical and electronics. To enable the manufacturing of complex multifunctional 3D objects, SMPs are often coupled with other functional polymers or fillers during or before the 3D printing process. This review highlights the 4D printing of state-of-the-art multi-component SMP formulations. Commonly used 4D printing technologies such as material extrusion techniques including fused filament fabrication (FFF) and direct ink writing (DIW), as well as vat photopolymerization techniques such as stereolithography (SLA), digital light processing (DLP), and multi-photon polymerization (MPP), are discussed. Different multicomponent SMP systems, their actuation methods, and potential applications of the 3D printed objects are reviewed. Finally, current challenges and prospects for 4D printing technology are summarized.

Four-dimensional (4D) printing, an evolution of additive manufacturing (AM), integrates stimuli-responsive materials like thermal-induced shape memory polymers (TSMPs) to enable programmable, time-dependent transformations in structures. This review systematically examines recent advancements in TSMPs, 4D printing technologies, and fabrication strategies, emphasizing their interdisciplinary convergence and applications. TSMPs, with their unique phase-separated microstructures, modulus disparity, and tailorable recovery behaviors, form the foundation of 4D-printed systems, enabling innovations in aerospace, healthcare, and soft robotics [1–3, 33–45]. Key printing methods—including fused deposition modeling (FDM), direct ink writing (DIW), PolyJet, stereolithography (SLA), and digital light processing (DLP)—are analyzed for their strengths and limitations. FDM dominates due to cost-effectiveness but faces challenges in resolution and anisotropy [88, 91–93], while SLA and DLP offer high precision and speed but require material optimization [105, 111–115]. Advanced fabrication strategies, such as localized TSMP printing, composite reinforcement with carbon nanotubes or Fe 3O 4 particles, and sacrificial mold templating, expand design possibilities for multi-functional and multi-scale structures [117–120, 140–144]. Despite progress, challenges persist, including environmental sensitivity of TSMPs, interlayer bonding in AM, and dynamic modeling of non-equilibrium thermal responses [74, 77, 146]. Future directions focus on multi-responsive materials, machine learning-driven constitutive models, and sustainable bio-based formulations to address scalability and cyclic durability [31, 77, 147–149]. By bridging material science, computational modeling, and advanced manufacturing, this work provides a roadmap for harnessing 4D-printed TSMPs in real-world applications, from self-deploying biomedical devices to adaptive aerospace systems [28, 85, 137].

PurposeFabrication of customized products in low volume through conventional manufacturing incurs a high cost, longer processing time and huge material waste. Hence, the concept of additive manufacturing (AM) comes into existence and fused deposition modelling (FDM), is at the forefront of researches related to polymer-based additive manufacturing. The purpose of this paper is to summarize the research works carried on the applications of FDM.Design/methodology/approachIn the present paper, an extensive review has been performed related to major application areas (such as a sensor, shielding, scaffolding, drug delivery devices, microfluidic devices, rapid tooling, four-dimensional printing, automotive and aerospace, prosthetics and orthosis, fashion and architecture) where FDM has been tested. Finally, a roadmap for future research work in the FDM application has been discussed. As an example for future research scope, a case study on the usage of FDM printed ABS-carbon black composite for solvent sensing is demonstrated.FindingsThe printability of composite filament through FDM enhanced its application range. Sensors developed using FDM incurs a low cost and produces a result comparable to those conventional techniques. EMI shielding manufactured by FDM is light and non-oxidative. Biodegradable and biocompatible scaffolds of complex shapes are possible to manufacture by FDM. Further, FDM enables the fabrication of on-demand and customized prosthetics and orthosis. Tooling time and cost involved in the manufacturing of low volume customized products are reduced by FDM based rapid tooling technique. Results of the solvent sensing case study indicate that three-dimensional printed conductive polymer composites can sense different solvents. The sensors with a lower thickness (0.6 mm) exhibit better sensitivity.Originality/valueThis paper outlines the capabilities of FDM and provides information to the user about the different applications possible with FDM.

The complexity of surgical treatments for large-area soft tissue injuries makes placing large implants into injury sites challenging. Aliphatic polyesters are often used for scaffold preparation in tissue engineering owing to their excellent biodegradability and biocompatibility. Scaffolds with shape-memory effect (SME) can also avoid large-volume trauma during the implantation. However, the complexity and diversity of diseases require more adaptable and precise processing methods. Four-dimensional (4D) printing, a booming smart material additive manufacturing technology, provides a new opportunity for developing shape memory scaffolds. With the aim of personalized or patient-adaptable soft tissues such as blood vessels, we developed a feasible strategy for fabricating scaffolds with fine architectures using 4D printing crosslinkable shape memory linear copolyesters using fused deposition modeling (FDM). To overcome the weak bonding strength of each printed layer during FDM, a catalyst-free photo-crosslinkable functional group derived from biocompatible cinnamic acid was embedded into the linear copolyesters as in situ crosslinking points during FDM printing. Under ultraviolet-assisted irradiation, the resulting 4D scaffold models demonstrated excellent SME, desirable mechanical performance, and good stability in a water environment owing to the chemical bonding between each layer. Moreover, the excellent biocompatibility of the scaffold was evaluated in vitro and in vivo. The developed composite scaffolds could be used for minimally invasive soft tissue repair.

Four-dimensional (4D) printing, a state-of-the-art additive manufacturing technology, enables the creation of objects capable of changing shape, properties, or functionality over time in response to external stimuli. However, the lack of effective remote control and reliance on a single actuation method pose significant challenges, limiting its applications in various fields. This study aims to address these limitations by developing a novel multi-responsive nanocomposite. By coating near-infrared light (NIR)-responsive polypyrrole (PPy) onto the surface of magnetic iron oxide (Fe2O3) nanoparticles (NPs), multi-responsive PPy@Fe2O3 NPs were synthesized. Doping PPy@Fe2O3 into a thermo-responsive shape memory polymer (SMP) matrix created a nanocomposite with excellent NIR and magnetic responsiveness, enabling dynamic, remote-controlled shape transformation of printed objects with precise timing and positioning using NIR and a magnetic field. Using the nanocomposite, a proof-of-concept semi-tubular construct was fabricated to evaluate its controllable transformation capability and assess the potential for modulating neural stem cell (NSC) behaviors. Furthermore, three proof-of-concept smart robots with distinct features were designed and fabricated for cargo delivery in diverse scenarios and different purposes. Importantly, all complex operations of these robots were remotely controlled using NIR illumination and an external magnetic field. This novel approach demonstrates significant progress in addressing the key challenges of remote control and actuation in 4D printing, highlighting its potential for enhanced versatility and functionality across various applications.

4D printing is a pioneer field to produce functional smart devices. The combination of 3D printing and smart material is called as 4D printing. The extra dimension refers to time in order to shape transformation of the printed part during time. FDM is a universal process to 3D printing of thermoplastic polymers. Therefore, for successful and typical 4D printing a deep understanding of every aspect of shape memory polymers especially thermoplastic polymers is necessary. So, in this chapter, shape memory polymers, printing preparation such as filament production and FDM printing parameters, finally applications, previous finding and functional printed parts by FDM have been studied detailed.

Hybrid hinge structure with elastic hinge on self-folding of 4D printing using a fused deposition modeling 3D printer

Although several force application concepts are known that can be used to deform shape memory polymers (SMPs) within the scope of programming, controlled deformation is challenging in the case of samples with a cylinder-like shape, which need to be homogeneously compressed starting from the lateral surface. To solve this problem, this contribution follows a material approach that takes advantage of four-dimensional (4D) printing. Fused filament fabrication (FFF) was used as an additive manufacturing (AM) technique to produce a thermoresponsive tool in a cylindrical shape from a polyether urethane (PEU) having a glass transition temperature (Tg) close to 55 °C, as determined by differential scanning calorimetry (DSC). Once it was 4D-printed, a sample of laser cut polyester urethane urea (PEUU) foam with a cylindrical wall was placed inside of it. Subsequent heating to 75 °C and keeping that temperature constant for 15 min resulted in the compression of the foam, because the internal stresses of the PEU were transferred to the PEUU, whose soft segments were completely molten at 65 °C as verified by DSC. Upon cooling to -15 °C and thus below the offset temperature of the soft segment crystallization transition of the PEUU, the foam was fixed in its new shape. After 900 days of storage at temperatures close to 23 °C, the foam recovered its original shape upon reheating to 75 °C. In another experiment, a 4D-printed cylinder was put into hibernation for 900 days before its thermoresponsiveness was investigated. In the future, 4D-printed tools may be produced in many geometries, which fit well to the shapes of the SMPs to be programmed. Beyond programming SMP foams, transferring the forces released by 4D-printed tools to other programmable materials can further expand technical possibilities.

Hybrid IGA-FEA of fiber reinforced thermoplastic composites for forward design of AI-enabled 4D printing

A three-dimensional (3D) printing method has been suggested as a manufacturing tool for complex structures. However, 3D printed parts have poor mechanical properties compared to those fabricated by traditional methods such as injection and compression molding. To overcome the disadvantage, the 3D printing system of continuous carbon fiber reinforced shape memory polymer composites (SMPC) was constructed using a material extrusion type-3D printer. The two types of matrices were used; thermoplastics and thermosets. With regard to the matrix type, the different method was adjusted to each printer. In order to set the proper condition of 3D printing, the thermal and rheological properties of various SMP matrices were characterized. The process parameters, such as temperature and printing speed, were varied for optimizing the printing system. Then, the tensile specimens of SMPC were printed and their mechanical and shape memory properties were evaluated. The printed SMPC showed good mechanical properties compared to those of conventionally 3D printed polymer in the fiber direction. Their shape memory behavior and thermomechanical properties were characterized. Then, a complex 3D shapes composed of basic unit cells was designed considering the fiber orientation. The possibility of developing morphing structures using 3D printing of continuous carbon fiber reinforced SMPC was investigated.