4D printing of tracheal scaffold using shape-memory polymer composite

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.

Typical techniques for creating synthetic morphing structures suffer from a compromise between quick shape change and geometric complexity. A novel approach is proposed for encoding numerous shapes and forms by magneto-electroactive shape memory polymer composite (SMPC) structures and integrating sustainability with 4D printing (4DP) technology. Electrically driven, remote controllability, and quick reaction are the features of these sustainable composite structures. Low-cost 4D-printed SMPC structures can be programmed remotely at high temperatures to achieve multi-stable shapes and can snap repeatedly between all programmed temporary and permanent configurations. This allows for multiple designs in a single structure without wasting material. The strategy is based on a knowledge of SMPC mechanics, magnetic response, and the manufacturing idea underlying fused deposition modelling (FDM). Iron-filled magnetic polylactic acid (MPLA) and carbon black-filled conductive PLA (CPLA) composite materials are investigated in terms of microstructure properties, composite interface, and mechanical properties. Characterisation studies are carried out to identify how to control the structure with a low magnetic field. The shape morphing of magneto-electroactive SMPC structures is studied. FDM is used to 4D print MPLA and CPLA adaptive structures with 1D/2D-to-2D/3D shapeshifting by the magnetic field. The benefits of switchable multi-stable structures are reducing material waste and effort/energy and increasing efficiency in sectors such as packaging.Graphical

Shape memory polymers (SMPs) have emerged as a revolutionary class of smart materials with enormous potential for applications in engineering and science. This manuscript provides a comprehensive review, examining their processing techniques, compositions, characteristics, and applications. It also looks at different shape memory polymer materials, blends, and composites in a critical way by looking at their features and improved mechanical, thermal, electrical, and other properties. It discusses all reinforcements, such as carbon nanotubes, graphene, and metal nanoparticles, used in earlier studies and their impact on various shape memory composites and their properties. Recent trends in research related to shape memory polymer composites (SMPCs) have focused on providing solutions to these problems by adding fillers or reinforcements and/or combining them with other polymers. Further, it provides major applications of SMPS in biomedical, aerospace, smart textiles, sensors, and self-healing materials. A detailed review of all these applications, along with their challenges also discussed thoroughly. This review helps in providing a bridge between existing knowledge and future directions of SMPs and composites involve developing multi-stimuli responsive materials, improving material properties using hybrid reinforcements, developing complex shape recovery mechanisms, including self-healing and functional futures in emerging areas like biomedical, soft robotics, and other applications.

Personalized 4D printing of bioinspired tracheal scaffold concept based on magnetic stimulated shape memory composites

This paper is concerned about an investigation of mechanical and electrical conductive properties of carbon fiber fabric reinforced shape memory polymer composite (SMPC). The shape memory polymer (SMP) is a thermoset styrene-based resin. SMP is a promising smart material, which is under intensive investigation at present. Its primary advantages over other smart materials are the high strain capacity (200% reversible strain), low density and low cost etc.. But its major drawbacks are low strength, low modulus and low recovery stress. So the fiber reinforced SMPC was naturally considered to be investigated in this paper, which may overcome the disadvantages mentioned above. The investigation was conducted with experimental methods: Dynamic Mechanical Analyzer (DMA), static and mechanical cycle loading tests, microscope observation of microstructural deformation mechanism, conductivity and shape recovery tests. Results indicated that SMPC showed higher glass transition temperature (Tg) than neat SMP and improved the storage modulus, bending modulus, strength and resistance against relaxation and creep. Both fiber microbuckling and fracture of SMPC were observed after the static 3-ponit bending test at the constant room temperature. SMPC showed favorable recovery performances during thermomechanical cycles of the bending recovery test and the fiber microbuckling was obvious. Moreover, the conductive SMPC of this study experienced low electrical resistivity and performed a good shape memory effect during numerous thermomechanical cycles.

4 - 4D-printed low-voltage electroactive polymers modeling and fabrication

Precise stimulation of near-infrared light responsive shape-memory polymer composites using upconversion particles with photothermal capability

The development of shape-memory polymer composites (SMPCs) enables high recovery stress levels as well as novel functions such as electrical conductivity, magnetism, and biofunctionality. In this review chapter the substantial enhancement in mechanical properties of shape-memory polymers (SMPs) by incorporating small amounts of stiff fillers will be highlighted exemplarily for clay and polyhedral oligomeric silsesquioxanes (POSS). Three different functions resulting from adding functional fillers to SMP-matrices will be introduced and discussed: magnetic SMPCs with different types of magnetic nanoparticles, conductive SMPCs based on carbon nanotubes (CNTs), carbon black (CB), short carbon fiber (SCF), and biofunctional SMPCs containing hydroxyapatite (HA). Indirect induction of the shape-memory effect (SME) was realized for magnetic and conductive SMPCs either by exposure to an alternating magnetic field or by application of electrical current. Major challenges in design and fundamental understanding of polymer composites are the complexity of the composite structure, and the relationship between structural parameters and properties/functions, which is essential for tailoring SMPCs for specific applications. Therefore the novel functions and enhanced properties of SMPCs will be described considering the micro-/nanostructural parameters, such as dimension, shape, distribution, volume fraction, and alignment of fillers as well as interfacial interaction between the polymer matrix and dispersed fillers. Finally, an outlook is given describing the future challenges of this exciting research field as well as potential applications including automotive, aerospace, sensors, and biomedical applications.

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].

Influence of thermoplastic polyurethane (TPU) and printing parameters on the thermal and mechanical performance of polylactic acid (PLA) / thermoplastic polyurethane (TPU) polymer

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.

Shape memory polymers (SMPs) are a new type of smart material, they perform large reversible deformation with a certain external stimulus (e.g., heat and electricity). The properties (e.g., stiffness, strength and other mechanically static or quasi-static load-bearing capacity) are primarily considered for conventional resin-based composite materials which are mainly used for structural materials. By contrast, the mechanical actuating performance with finite deformation is considered for the shape memory polymers and their composites which can be used for both structural materials and functional materials. For shape memory polymers and their composites, the performance of active deformation is expected to further promote the development in smart active deformation structures, such as deployable space structures and morphing wing aircraft. The shape memory polymer composites (SMPCs) are also one type of High Strain Composite (HSC). The space deployable structures based on carbon fiber reinforced shape memory polymer composites (SMPCs) show great prospects. Considering the problems that SMPCs are difficult to meet the practical applications in space deployable structures in the recent ten years, this paper aims to research the mechanics of deformation, and failure of SMPCs. In the overall view of the shape memory polymer material’s nonlinearity (nonlinearity and stress softening in the process of pre-deformation and recovery, relaxation in storage process, irreversible deformation), by the multiple verifications among theory, finite element and experiments, one obtains the deformation and mechanism for the process of “pre-deformation, energy storage and actuation and its non-fracture constraint domain. Then, the parameters of SMPCs will be optimized. Theoretical analysis is realized by the strain energy function, additionally considering the interaction strain energy between the fiber and the matrix. For the common resin-based or soft-material-based composites under pure bending deformation, we expect to uniformly explain the whole process of buckling occurrence, evolution and finally failure, especially for the early evolution characteristics of fiber microbuckling inside the microstructures. The research results are meaningful for the practical applications for SMPC deployable structures in space. Considering the deformation mechanisms of SMPCs, the local post-microbuckling is required for the unidirectional fiber reinforced composite materials, at the conditions of its large geometrical deflection. The cross section of SMPC is divided into three areas: non-buckling stretching area, non-buckling compressive area, and buckling compressive area. Three variables are considered: critical buckling position, and neutral plane, the fiber buckling half-wavelength. Considering the condition of the small strain and large displacement, the strain energy expression of the SMP/fiber system was derived, which contains two types, e.g., strain energy of SMP and fiber. According to the minimum energy principle, the expression for all key parameters were derived, including the critical buckling curvature, neutral plane position, the buckling half-wavelength, fiber buckling amplitude, and strain.

Shape memory property and mechanism of the knitting-fabric reinforced epoxy composites subjected to tensile loading

This work presents the development and characterization of multiresponsive shape memory polymer composites based on thermoplastic polyurethane (TPU), poly( ϵ -caprolactone) (PCL), and Fe 3 O 4 particles, targeting applications in 4D printing. The TPU/PCL blend provides mechanical strength, flexibility, and a pronounced shape memory effect, while Fe 3 O 4 enables remote activation under near-infrared (NIR) light and microwave radiation. Composites containing 15, 20, 25, and 30 phr of Fe 3 O 4 , derived from the TPU/PCL (50/50) blend, were compared to the unloaded blend. The shape memory behavior assessed via dynamic mechanical thermal analysis (DMTA) revealed excellent shape fixity (∼100%) and recovery (∼80%), with a slight decrease in recovery ratio (from 83% to 79%) as Fe 3 O 4 content increased. Under NIR and microwave stimuli, recovery efficiency improved with higher Fe 3 O 4 loading, reducing total recovery time (60–46 s) and activation time (22–11 s), with saturation above 25 phr. Self-healing properties were also evaluated, showing nearly complete repair in 120 s under NIR and microwave stimulation, while conventional oven heating required longer times (180 s) and was less effective. Additionally, adhesion tests demonstrated that after bonding, the samples retained 50% of their original tensile strength, and failure occurred outside the bonded region, indicating strong interfacial adhesion. Overall, the composites exhibited excellent multistimuli shape memory behaviour, rapid remote actuation, and strong self-healing, highlighting their potential for advanced smart materials and 4D-printed functional structures.

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.